EP4127068B1 - Low chloride mineral wool product - Google Patents
Low chloride mineral wool product Download PDFInfo
- Publication number
- EP4127068B1 EP4127068B1 EP20718606.5A EP20718606A EP4127068B1 EP 4127068 B1 EP4127068 B1 EP 4127068B1 EP 20718606 A EP20718606 A EP 20718606A EP 4127068 B1 EP4127068 B1 EP 4127068B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- water
- binder composition
- mineral fibre
- fibre product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000011490 mineral wool Substances 0.000 title description 8
- 229910001578 chloride mineral Inorganic materials 0.000 title 1
- 239000011230 binding agent Substances 0.000 claims description 260
- 229920005610 lignin Polymers 0.000 claims description 239
- 239000000203 mixture Substances 0.000 claims description 212
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 199
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 148
- 239000011707 mineral Substances 0.000 claims description 148
- 238000000034 method Methods 0.000 claims description 142
- 239000000835 fiber Substances 0.000 claims description 109
- 238000007254 oxidation reaction Methods 0.000 claims description 82
- 230000003647 oxidation Effects 0.000 claims description 77
- 230000008569 process Effects 0.000 claims description 73
- 239000004014 plasticizer Substances 0.000 claims description 54
- 239000004971 Cross linker Substances 0.000 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 44
- 238000009413 insulation Methods 0.000 claims description 37
- -1 siloxanes Chemical class 0.000 claims description 35
- 229920005611 kraft lignin Polymers 0.000 claims description 31
- 239000008213 purified water Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims description 25
- 239000004575 stone Substances 0.000 claims description 25
- 239000012633 leachable Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 21
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 21
- 150000001412 amines Chemical class 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 210000002268 wool Anatomy 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 16
- 235000019198 oils Nutrition 0.000 claims description 15
- 235000000346 sugar Nutrition 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 239000008399 tap water Substances 0.000 claims description 10
- 235000020679 tap water Nutrition 0.000 claims description 10
- 229920001732 Lignosulfonate Polymers 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 230000009972 noncorrosive effect Effects 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002557 mineral fiber Substances 0.000 claims description 8
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 150000008163 sugars Chemical class 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 6
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000010962 carbon steel Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 150000003951 lactams Chemical class 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000003784 tall oil Substances 0.000 claims description 5
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910000963 austenitic stainless steel Inorganic materials 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 125000005498 phthalate group Chemical class 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 claims description 4
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000008064 anhydrides Chemical group 0.000 claims description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 2
- OGFKTAMJLKHRAZ-UHFFFAOYSA-N 2,2-dimethoxyacetaldehyde Chemical compound COC(OC)C=O OGFKTAMJLKHRAZ-UHFFFAOYSA-N 0.000 claims description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
- RLEBXPWQNYAXQH-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexaethoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CCON(OCC)C1=NC(N(OCC)OCC)=NC(N(OCC)OCC)=N1 RLEBXPWQNYAXQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 150000003869 acetamides Chemical class 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 2
- 150000004648 butanoic acid derivatives Chemical class 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 claims description 2
- 150000002193 fatty amides Chemical class 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 150000001261 hydroxy acids Chemical class 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004819 silanols Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 150000003445 sucroses Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-M valerate Chemical class CCCCC([O-])=O NQPDZGIKBAWPEJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 112
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 104
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 85
- 229910021529 ammonia Inorganic materials 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000007787 solid Substances 0.000 description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 35
- 239000000463 material Substances 0.000 description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- 238000002156 mixing Methods 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 18
- 239000000523 sample Substances 0.000 description 18
- 239000004202 carbamide Substances 0.000 description 17
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
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- 239000003513 alkali Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 150000004756 silanes Chemical class 0.000 description 12
- 239000003607 modifier Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
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- 150000001720 carbohydrates Chemical class 0.000 description 9
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- 230000008901 benefit Effects 0.000 description 8
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
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- 238000004448 titration Methods 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000013341 scale-up Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
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- OKRNLSUTBJUVKA-UHFFFAOYSA-N n,n,n',n'-Tetrakis(2-hydroxyethyl)adipamide Chemical compound OCCN(CCO)C(=O)CCCCC(=O)N(CCO)CCO OKRNLSUTBJUVKA-UHFFFAOYSA-N 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- 238000007865 diluting Methods 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/005—Lignin
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/02—Moisture-responsive characteristics
- D10B2401/021—Moisture-responsive characteristics hydrophobic
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
Definitions
- the present invention relates to a mineral fibre product, and a use of a mineral fibre product.
- Mineral fibre products also termed mineral wool products generally comprise mineral fibres (also termed as man-made vitreous fibres (MMVF)) such as, e.g., glass fibres, ceramic fibres, basalt fibres, slag fibres, and stone fibres (rock fibres), which are bonded together by a cured thermoset polymeric binder material.
- mineral fibres also termed as man-made vitreous fibres (MMVF)
- MMVF man-made vitreous fibres
- bonded mineral fibre mats are generally produced by converting a melt made of suitable raw materials to fibres in conventional manner, for instance by a spinning cup process or by a cascade rotor process.
- the fibres are blown into a forming chamber and, while airborne and while still hot, are sprayed with a binder solution and randomly deposited as a mat or web onto a travelling conveyor.
- the fibre mat is then transferred to a curing oven where heated air is blown through the mat to cure the binder and rigidly bond the mineral fibres together.
- the binder resins of choice have been phenol-formaldehyde resins which can be economically produced and can be extended with urea prior to use as a binder.
- the existing and proposed legislation directed to the lowering or elimination of formaldehyde emissions have led to the development of formaldehyde-free binders such as, for instance, the binder compositions based on polycarboxy polymers and polyols or polyamines, such as disclosed in EP-A-583086 , EP-A-990727 , EP-A-1741726 , US-A-5,318,990 and US-A-2007/0173588 .
- non-phenol-formaldehyde binders are the addition/-elimination reaction products of aliphatic and/or aromatic anhydrides with alkanolamines, e.g., as disclosed in WO 99/36368 , WO 01/05725 , WO 01/96460 , WO 02/06178 , WO 2004/007615 and WO 2006/061249 .
- These binder compositions are water soluble and exhibit excellent binding properties in terms of curing speed and curing density.
- WO 2008/023032 discloses urea-modified binders of that type which provide mineral wool products having reduced moisture take-up.
- WO 2016/120576 describes ammonium lighosulphonates as binder and FR-2976584 Ignosulphonic acid as binder.
- a further effect in connection with previously known aqueous binder compositions from mineral fibres is that at least the majority of the starting materials used for the productions of these binders stem from fossil fuels.
- CUI Corrosion Under Insulation
- Corrosion occurs in the presence of water and oxygen. If the equipment or piping such as steelwork under insulation remains dry there is no corrosion problem. However, keeping insulation dry can be difficult. A certain type of corrosion can be caused or supported by water-soluble chlorides.
- Prior art binder compositions for mineral fibres can include significant amounts of water-soluble chlorides. Accordingly, the mineral fibre product itself can contribute to the corrosion of the insulated parts.
- the risk of corrosion under insulation of carbon steel is considered high in the temperature range of 50 to 175°C and extreme in cyclic temperature service between -20 and 320°C.
- the most frequently occurring types of CUI are general and pitting corrosion of carbon steel which may occur if wet insulation comes in contact with carbon steel, and external stress corrosion tracking (ESCT) of austenitic stainless steel, which is a specific type of corrosion mainly caused by the action of water-soluble chloride
- a further object of the present invention was to provide a use of such mineral fibre product.
- a mineral fibre product comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- a mineral fibre product comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- a method for the manufacture of a mineral fibre product comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001, the method comprising the steps of
- a hollow object covered with a mineral fibre product as a thermal and/or acoustic insulation wherein the mineral fibre product comprises mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- the inventors have found that it is possible to use a mineral fibre product as a low corrosive or even non-corrosive thermal and/or acoustic insulation, when a binder composition based on oxidized lignin is used for the mineral fibre product.
- This binder composition has a surprisingly low water leachable chloride content.
- the mineral fibre product of the invention comprises mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001, wherein the water leachable chloride content is preferably less than 6 mg/kg in accordance with EN 13468:2001.
- the water leachable chloride content of the mineral fibre product is measured according to EN 13468:2001.
- EN 13468:2001 inter alia relates to the determination of trace quantities of water soluble chloride in thermal insulating products for building equipment and industrial installations.
- the standard specifies the equipment and procedures for determining trace quantities of the water soluble chloride in an aqueous extract of the product. Reference is made to this standard for the details.
- the water leachable chloride content is given in mg chloride per kg mineral fibre product. Referring to table 1 in the EN standard, 100°C and 0,5h for leaching is used. Sample preparation according to 7.2.1 of EN 13468. Analysis according to 7.2.2.2 of EN 13468 (ion chromatography determination).
- the mineral fibre products of the present invention have a surprisingly low water leachable chloride content. This is even true when non-purified water such as tap water or process water is used for preparing the non-cured binder composition. As known by the skilled person, non-purified water can contain considerable amounts of chloride.
- the present inventors believe that that the low water leachable chloride content of the mineral fibre products of the invention, even if tap water or process water is used for preparing the binder composition, is at least partly based on a capture of chloride ions within the binder matrix based on oxidized lignin. This capture foreclose leaching of the chloride so that it is not available for corrosive activity.
- the uncured binder composition is an aqueous binder composition.
- the water contained in the aqueous binder composition may be purified water, non-purified water or a combination of purified water and non-purified water added.
- the non-cured binder composition is an aqueous binder composition, wherein at least part of the water or the total water contained in the aqueous binder composition is non-purified water, the other part of the water, if any, being purified water.
- Purified water is generally water that has been mechanically filtered or processed to remove impurities and make it suitable for use. Distilled water has been the most common form of purified water, but, in recent years, water is more frequently purified by other processes including capacitive deionization, reverse osmosis, carbon filtering, microfiltration, ultrafiltration, ultraviolet oxidation, or electrodeionization. It is preferred that the purified water used in the non-cured binder composition has a chloride content of less than 10 mg/L, preferably less than 5 mg/L.
- non-purified water is tap water, rain water, process water or a combination thereof.
- the chloride content of tap water and rain water is generally in the range of 10-200 mg/L.
- the chloride content of process water is generally in the range of 25-200 mg/L chloride. It is preferred that the non-purified water used in the non-cured binder composition can have a chloride content of at least 10 mg/L, such as a chloride content in the range of 10-200 mg/L.
- the proportion of non-purified water added can be in the range of 0 to 100 wt.-%, preferably 30 to 100 wt.-%, most preferred 50 to 100 wt.-%, based on the total weight of water contained in the non-cured binder composition, the other proportion, if any, being purified water.
- the binder composition In a production plant, the binder composition is usually produced in a concentrated form, i.e. the water content is kept low. After delivery, the concentrated binder composition is diluted by addition of water on site of the mineral fibre production to a suitable viscosity. The diluted binder composition is contacted with the mineral fibres and is cured to produce the mineral fibre product. It is a benefit of the present invention that non-purified water such as tap water, rain water or process water can be used for diluting the concentrated binder composition and nevertheless products with low water leachable chloride content are achieved.
- non-purified water such as tap water, rain water or process water can be used for diluting the concentrated binder composition and nevertheless products with low water leachable chloride content are achieved.
- the binders according to the present invention are formaldehyde free.
- the term "formaldehyde free” is defined to characterize a mineral wool product where the emission is below 5 ⁇ g/m 2 /h of formaldehyde from the mineral wool product, preferably below 3 ⁇ g/m 2 /h.
- the test is carried out in accordance with ISO 16000 for testing aldehyde emissions.
- the non-cured binder composition for preparing of the mineral fibre product according to the present invention comprises one or more oxidized lignins as a component (i).
- Component (i) is in form of one or more oxidized lignins.
- Lignin, cellulose and hemicellulose are the three main organic compounds in a plant cell wall. Lignin can be thought of as the glue, that holds the cellulose fibres together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, second only to cellulose, and is estimated to represent as much as 20-30% of the total carbon contained in the biomass, which is more than 1 billion tons globally.
- Fig. 1 shows a section from a possible lignin structure.
- lignin There are at least four groups of technical lignins available in the market. These four groups are shown in Fig. 3 .
- a possible fifth group, Biorefinery lignin is a bit different as it is not described by the extraction process, but instead by the process origin, e.g. biorefining and it can thus be similar or different to any of the other groups mentioned.
- Each group is different from each other and each is suitable for different applications.
- Lignin is a complex, heterogenous material composed of up to three different phenyl propane monomers, depending on the source.
- Softwood lignins are made mostly with units of coniferyl alcohol, see fig. 2 and as a result, they are more homogeneous than hardwood lignins, which has a higher content of syringyl alcohol, see fig. 2 .
- the appearance and consistency of lignin are quite variable and highly contingent on process.
- Lignosulfonate from the sulfite pulping process remains the largest commercial available source of lignin, with capacity of 1.4 million tonnes. But taking these aside, the kraft process is currently the most used pulping process and is gradually replacing the sulfite process. An estimated 78 million tonnes per year of lignin are globally generated by kraft pulp production but most of it is burned for steam and energy. Current capacity for kraft recovery is estimated at 160,000 tonnes, but sources indicate that current recovery is only about 75,000 tonnes. Kraft lignin is developed from black liquour, the spent liquor from the sulfate or kraft process. At the moment, 3 well-known processes are used to produce the kraft lignin: LignoBoost, LignoForce and SLRP.
- the kraft process introduces thiol groups, stilbene while some carbohydrates remain. Sodium sulphate is also present as an impurity due to precipitation of lignin from liquor with sulphuric acid but can potentially be avoided by altering the way lignin is isolated.
- the kraft process leads to high amount of phenolic hydroxyl groups and this lignin is soluble in water when these groups are ionized (above pH ⁇ 10).
- kraft lignin is generally higher in purity than lignosulfonates.
- the molecular weight are 1000-3000 g/mol.s
- Soda lignin originates from sodium hydroxide pulping processes, which are mainly used for wheat straw, bagasse and flax. Soda lignin properties are similar to kraft lignins one in terms of solubility and T g . This process does not utilize sulphur and there is no covalently bound sulphur. The ash level is very low. Soda lignin has a low solubility in neutral and acid media but is completely soluble at pH 12 and higher.
- the lignosulfonate process introduces large amount of sulphonate groups making the lignin soluble in water but also in acidic water solutions.
- Lignosulfonates has up to 8% sulfur as sulphonate, whereas kraft lignin has 1-2% sulfur, mostly bonded to the lignin.
- the molecular weight of lignosulfonate is 15.000-50.000 g/mol. This lignin contains more leftover carbohydrates compared to other types and has a higher average molecular weight.
- the typical hydrophobic core of lignin together with large number of ionized sulphonate groups make this lignin attractive as a surfactant and it often finds application in dispersing cement etc.
- a further group of lignins becoming available is lignins resulting from biorefining processes in which the carbohydrates are separated from the lignin by chemical or biochemical processes to produce a carbohydrate rich fraction. This remaining lignin is referred to as biorefinery lignin. Biorefineries focus on producing energy, and producing substitutes for products obtained from fossil fuels and petrochemicals as well as lignin. The lignin from this process is in general considered a low value product or even a waste product mainly used for thermal combustion or used as low grade fodder or otherwise disposed of.
- Organosolv lignin availability is still considered on the pilot scale.
- the process involves extraction of lignin by using water together with various organic solvents (most often ethanol) and some organic acids.
- An advantage of this process is the higher purity of the obtained lignin but at a much higher cost compared to other technical lignins and with the solubility in organic solvents and not in water.
- lignin is used to replace oil derived chemicals, such as phenol in phenolic resins in binder applications or in bitumen. It is also used as cement and concrete additives and in some aspects as dispersants.
- the cross-linking of a polymer in general should provide improved properties like mechanical, chemical and thermal resistance etc.
- Lignin is especially abundant in phenolic and aliphatic hydroxyl groups that can be reacted leading to cross-linked structure of lignin.
- Different lignins will also have other functional groups available that can potentially be used. The existence of these other groups is largely dependent on the way lignin was separated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in lignosulfonate etc.) depending on the source.
- binder compositions for mineral fibres can be prepared which allow excellent properties of the mineral fibre product produced.
- the component (i) is in form of one or more oxidized kraft lignins.
- the component (i) is in form of one or more oxidized soda lignins.
- the component (i) is in form of one or more ammonia-oxidized lignins.
- ammonia-oxidized lignins is to be understood as a lignin that has been oxidized by an oxidation agent in the presence of ammonia.
- AOL ammonia-oxidized lignin
- ammonia is partially or fully replaced by an alkali metal hydroxide, in particular sodium hydroxide and/or potassium hydroxide.
- a typical oxidation agent used for preparing the oxidized lignins is hydrogen peroxide.
- the ammonia-oxidized lignin comprises one or more of the compounds selected from the group of ammonia, amines, hydroxides or any salts thereof.
- the component (i) is having a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i).
- component (i), i.e. the one or more oxidized lignins may be present in an amount of 25 to 95 wt.-%, such as 30 to 90 wt.-%, such as 35 to 85 wt.-%, based on the dry weight of the binder composition.
- the component (i) is having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups.
- the carboxylic acid group content of the oxidized lignins plays an important role in the surprising advantages of the binder compositions, preferably the aqueous binder compositions, for mineral fibres according to the present invention.
- the carboxylic acid group of the oxidized lignins improve the cross-linking properties and therefore allow better mechanical properties of the cured mineral fibre products.
- Optional component (ii) is in form of one or more cross-linkers.
- the component (ii) comprises in one embodiment one or more cross-linkers selected from ⁇ -hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers.
- ⁇ -hydroxyalkylamide-cross-linkers is a curing agent for the acid-functional macromolecules. It provides a hard, durable, corrosion resistant and solvent resistant cross-linked polymer network. It is believed the ⁇ -hydroxyalkylamide cross-linkers cure through esterification reaction to form multiple ester linkages.
- the hydroxy functionality of the ⁇ -hydroxyalkylamide-cross-linkers should be an average of at least 2, preferably greater than 2 and more preferably 2-4 in order to obtain optimum curing response.
- Oxazoline group containing cross-linkers are polymers containing one of more oxazoline groups in each molecule and generally, oxazoline containing crosslinkers can easily be obtained by polymerizing an oxazoline derivative.
- the patent US6818699 B2 provides a disclosure for such a process.
- the component (ii) is an epoxidised oil based on fatty acid triglyceride.
- epoxidised oils based on fatty acid triglycerides are not considered hazardous and therefore the use of these compounds in the binder compositions according to the present invention do not render these compositions unsafe to handle.
- the component (ii) is a molecule having 3 or more epoxy groups.
- the component (ii) is one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
- a low Tg acrylic based polymer such as a low Tg vinyl based polymer, such as low Tg polyether
- reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
- component (ii) is selected from the group consisting of cross-linkers taking part in a curing reaction, such as hydroxyalkylamide, alkanolamine, a reaction product of an alkanolamine and a polycarboxylic acid.
- cross-linkers taking part in a curing reaction, such as hydroxyalkylamide, alkanolamine, a reaction product of an alkanolamine and a polycarboxylic acid.
- the reaction product of an alkanolamine and a polycarboxylic acid can be found in US6706853B1 .
- the very advantageous properties of the binder compositions, preferably the aqueous binder compositions, used according to the present invention are due to the interaction of the oxidized lignins used as component (i) and the cross-linkers mentioned above. It is believed that the presence of carboxylic acid groups in the oxidized lignins enable the very effective cross-linking of the oxidized lignins.
- the component (ii) is one or more cross-linkers selected from the group consisting of multifunctional organic amines such as an alkanolamine, diamines, such as hexamethyldiamine, triamines.
- the component (ii) is one or more cross-linkers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
- the component (ii) is one or more fatty amides.
- the component (ii) is one or more cross-linkers selected from the group consisting of dimethoxyethanal, glycolaldehyde, glyoxalic acid.
- the component (ii) is one or more cross-linkers selected from polyester polyols, such as polycaprolactone.
- the component (ii) is one or more cross-linkers selected from the group consisting of starch, modified starch, CMC.
- the component (ii) is one or more cross-linkers in form of aliphatic multifunctional carbodiimides
- the component (ii) is one or more cross-linkers selected from melamine based cross-linkers, such as a hexakis(methylmethoxy)melamine (HMMM) based cross-linkers.
- melamine based cross-linkers such as a hexakis(methylmethoxy)melamine (HMMM) based cross-linkers.
- Picassian XL 701, 702, 725 (Stahl Polymers), such as ZOLDINE ® XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).
- component (ii) is Primid XL552, which has the following structure:
- Component (ii) can also be any mixture of the above mentioned compounds.
- the binder composition preferably the aqueous binder composition, used according to the present invention comprises component (ii) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of component (i).
- Optional component (iii) is in form of one or more plasticizers.
- component (iii) is in form of one or more plasticizers selected from the group consisting of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
- polyols such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers,
- component (iii) is in form of one or more plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin like vanillin, acetosyringone, solvents used as coalescing agents like alcohol ethers, polyvinyl alcohol.
- plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin like vanillin, acetosyringone, solvents used as coalescing agents like alcohol ethers, polyvinyl alcohol.
- component (iii) is in form of one or more non-reactive plasticizer selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or other esters, solvents used as coalescing agents like alcohol ethers, acrylic polymers, polyvinyl alcohol.
- non-reactive plasticizer selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or other esters, solvents used as coalescing agents like alcohol ethers, acrylic polymers, polyvinyl alcohol.
- component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and/or vanillic acid and/or ferullic acid, polyurethane dispersions, acrylic based polymers with free carboxy groups, compounds with a structure similar to lignin like vanillin, acetosyringone.
- carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and/or vanillic acid and/or ferullic acid
- polyurethane dispersions acrylic based polymers with free carboxy groups, compounds with a structure similar to lignin like vanillin, acetosyringone.
- component (iii) is in form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.
- component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers.
- plasticizers having a boiling point of more than 100 °C, in particular 140 to 250 °C strongly improves the mechanical properties of the mineral fibre products according to the present invention although, in view of their boiling point, it is likely that these plasticizers will at least in part evaporate during the curing of the binders, preferably the aqueous binders, in contact with the mineral fibres.
- component (iii) comprises one or more plasticizers having a boiling point of more than 100 °C, such as 110 to 280 °C, more preferred 120 to 260 °C, more preferred 140 to 250 °C.
- the effectiveness of these plasticizers in the binder composition, preferably the aqueous binder composition, used according to the present invention is associated with the effect of increasing the mobility of the oxidized lignins during the curing process. It is believed that the increased mobility of the lignins or oxidized lignins during the curing process facilitates the effective cross-linking.
- component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50000 g/mol, in particular 150 to 4000 g/mol, more particular 150 to 1000 g/mol, preferably 150 to 500 g/mol, more preferably 200 to 400 g/mol.
- component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g/mol, in particular 4000 to 15000 g/mol, more particular 8000 to 12000 g/mol.
- component (iii) is capable of forming covalent bonds with component (i) and/or component (ii) during the curing process.
- a component would not evaporate and remain as part of the composition but will be effectively altered to not introduce unwanted side effects e.g. water absorption in the cured product.
- Non-limiting examples of such a component are caprolactone and acrylic based polymers with free carboxyl groups.
- component (iii) is selected from the group consisting of fatty alcohols, monohydroxy alcohols, such as pentanol, stearyl alcohol.
- component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxylates such as ethoxylates such as butanol ethoxylates, such as butoxytriglycol.
- component (iii) is selected from one or more propylene glycols.
- component (iii) is selected from one or more glycol esters.
- component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates.
- component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives such as alkyl or aryl substituted phenols.
- component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.
- component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates; such as tributylphosphates.
- plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates; such as tributylphosphates.
- component (iii) is selected from one or more hydroxy acids.
- component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides such as acetamides, benzamide, fatty acid amides such as tall oil amides.
- component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyldimethylammoniumchloride.
- component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil.
- component (iii) is in form of tall oil.
- component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.
- component (iii) is selected from one or more fatty acid methyl esters.
- component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucoseamides, sucrose esters, sorbitan esters.
- the inclusion of plasticizers in the binder composition, preferably the aqueous binder composition, used according to the present invention strongly improves the mechanical properties of the mineral fibre products according to the present invention.
- plasticizer refers to a substance that is added to a material in order to make the material softer, more flexible (by decreasing the glass-transition temperature Tg) and easier to process.
- Component (iii) can also be any mixture of the above mentioned compounds.
- component (iii) is present in an amount of 0.5 to 50, preferably 2.5 to 25, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).
- Binder composition preferably aqueous binder composition for mineral fibers comprising components (i) and (iia)
- the present invention is directed to a binder composition, preferably an aqueous binder composition, for mineral fibers comprising:
- the present inventors have found that the excellent binder properties can also be achieved by a two-component system which comprises component (i) in form of one or more oxidized lignins and a component (iia) in form of one or more modifiers, and optionally any of the other components mentioned above and below.
- component (iia) is a modifier in form of one or more compounds selected from the group consisting of epoxidised oils based on fatty acid triglycerides.
- component (iia) is a modifier in form of one or more compounds selected from molecules having 3 or more epoxy groups.
- component (iia) is a modifier in form of one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
- a low Tg acrylic based polymer such as a low Tg vinyl based polymer, such as low Tg polyether
- reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
- component (iia) is one or more modifiers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
- the component (iia) is one or more modifiers selected from aliphatic multifunctional carbodiimides.
- Component (iia) can also be any mixture of the above mentioned compounds.
- the present inventors believe that the excellent binder properties achieved by the binder composition for mineral fibers comprising components (i) and (iia), and optional further components, are at least partly due to the effect that the modifiers used as components (iia) at least partly serve the function of a plasticizer and a crosslinker.
- the binder composition preferably the aqueous binder composition, comprises component (iia) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of the component (i).
- the binder composition preferably the aqueous binder composition, used according to the present invention comprises further components.
- a catalyst selected from inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid, and/or any salts thereof such as sodium hypophosphite, and/or ammonium salts, such as ammonium salt
- the binder composition preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCl 2 , Mg(ClO 4 ) 2 , Sn[N(SO 2 -n-C 8 F 17 ) 2 ] 4 .
- a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCl 2 , Mg(ClO 4 ) 2 , Sn[N(SO 2 -n-C 8 F 17 ) 2 ] 4 .
- the binder composition preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from metal chlorides, such as KCI, MgCl 2 , ZnCl 2 , FeCl 3 and SnCl 2 .
- a catalyst selected from metal chlorides, such as KCI, MgCl 2 , ZnCl 2 , FeCl 3 and SnCl 2 .
- the binder composition preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from organometallic compounds, such as titanate-based catalysts and stannum based catalysts.
- the binder composition preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.
- chelating agents such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.
- the binder composition preferably the aqueous binder composition, used according to the present invention further comprises a further component (iv) in form of one or more silanes.
- the binder composition preferably the aqueous binder composition, used according to the present invention comprises a further component (iv) in form of one or more coupling agents, such as organofunctional silanes.
- component (iv) is selected from group consisting of organofunctional silanes, such as primary or secondary amino functionalized silanes, epoxy functionalized silanes, such as polymeric or oligomeric epoxy functionalized silanes, methacrylate functionalized silanes, alkyl and aryl functionalized silanes, urea funtionalised silanes or vinyl functionalized silanes.
- organofunctional silanes such as primary or secondary amino functionalized silanes
- epoxy functionalized silanes such as polymeric or oligomeric epoxy functionalized silanes, methacrylate functionalized silanes, alkyl and aryl functionalized silanes, urea funtionalised silanes or vinyl functionalized silanes.
- the binder composition preferably the aqueous binder composition, used according to the present invention further comprises a component (v) in form of one or more components selected from the group of ammonia, amines or any salts thereof.
- ammonia, amines or any salts thereof as a further component can in particular be useful when oxidized lignins are used in component (i), which oxidised lignin have not been oxidized in the presence of ammonia.
- the binder composition preferably the aqueous binder composition, used according to the present invention further comprises a further component in form of urea, in particular in an amount of 5 to 40 wt.-%, such as 10 to 30 wt.-%, 15 to 25 wt.-%, based on the dry weight of component (i).
- sucrose sucrose
- the binder composition preferably the aqueous binder composition, used according to the present invention further comprises a further component in form of one or more carbohydrates selected from the group consisting of sucrose and reducing sugars in an amount of 5 to 50 wt.-%, such as 5 to less than 50 wt.-%, such as 10 to 40 wt.-%, such as 15 to 30 wt.-% based on the dry weight of component (i).
- a further component in form of one or more carbohydrates selected from the group consisting of sucrose and reducing sugars in an amount of 5 to 50 wt.-%, such as 5 to less than 50 wt.-%, such as 10 to 40 wt.-%, such as 15 to 30 wt.-% based on the dry weight of component (i).
- a binder composition having a sugar content of 50 wt.-% or more, based on the total dry weight of the binder components is considered to be a sugar based binder.
- a binder composition having a sugar content of less than 50 wt.-%, based on the total dry weight of the binder components is considered a non-sugar based binder.
- the binder composition preferably the aqueous adhesive composition, used according to the present invention further comprises a further component in form of one or more surface active agents that are in the form of non-ionic and/or ionic emulsifiers such as polyoxyethylenes (4) lauryl ether, such as soy lecithin, such as sodium dodecyl sulfate.
- a further component in form of one or more surface active agents that are in the form of non-ionic and/or ionic emulsifiers such as polyoxyethylenes (4) lauryl ether, such as soy lecithin, such as sodium dodecyl sulfate.
- the binder composition preferably the aqueous binder composition, used according to the present invention consists essentially of
- the binder composition preferably the aqueous binder composition, used according to the present invention consists essentially of
- the mineral fibre product of the present invention can be prepared by a common method for producing a mineral fibre product by binding mineral fibres with the binder composition. Accordingly, the mineral fibre product of the present invention is preferably prepared by a method which comprises the steps of contacting mineral fibres with an uncured and preferably aqueous binder composition comprising one or more oxidized lignins.
- the present invention also relates to a method for the manufacture of a mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001, the method comprising the steps of
- the proportion of non-purified water added is in the range of 30 to 100 wt.-%, more preferably 50 to 100 wt.-%, based on the total weight of water contained in the non-cured binder composition.
- the water content in the non-cured aqueous binder composition is in the range of 40 to 90 wt.-%, preferably 60 to 85 wt.-%, based on the total weight of the non-cured aqueous binder composition
- the mineral fibre product obtained in the method according to the invention can have all features which are described herein for the inventive mineral fibre product so that reference is made thereto.
- the non-cured aqueous binder composition comprises
- the non-cured binder composition for use is prepared by diluting a concentrated form of the binder composition by addition of non-purified water.
- the uncured binder composition in mineral fibre product precursor such as a web where the mineral fibres are in contact with the binder composition is cured by a chemical and/or physical reaction of the binder components.
- the curing takes place in a curing device.
- the curing is carried out at temperatures from 100 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.
- the curing takes place in a conventional curing oven for mineral wool production operating at a temperature of from 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.
- the curing takes place for a time of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.
- curing takes place at a temperature of 150 to 250 °C for a time of 30 seconds to 20 minutes.
- the curing process may commence immediately after application of the binder to the fibres.
- the curing is defined as a process whereby the binder composition undergoes a physical and/or chemical reaction which in case of a chemical reaction usually increases the molecular weight of the compounds in the binder composition and thereby increases the viscosity of the binder composition, usually until the binder composition reaches a solid state.
- the curing process comprises drying by pressure.
- the pressure may be applied by blowing air or gas through/over the mixture of mineral fibres and binder.
- the present invention is directed to a mineral fibre product comprising mineral fibres in contact with a cured binder composition as described above, i.e. in contact with a cured binder resulting from the curing of the binder composition, preferably aqueous binder composition, described above.
- the mineral fibres employed may be any of man-made vitreous fibres (MMVF), glass fibres, ceramic fibres, basalt fibres, slag fibres, rock fibres, stone fibres and others. These fibres may be present as a wool product, e.g. like a stone wool product. In a preferred embodiment, the mineral fibres are stone fibres or stone wool, respectively.
- the man-made vitreous fibres can have any suitable oxide composition.
- the fibres can be glass fibres, ceramic fibres, basalt fibres, slag fibres or rock or stone fibres.
- the fibres are preferably of the types generally known as rock, stone or slag fibres, most preferably stone fibres.
- Stone fibres commonly comprise the following oxides, in percent by weight:
- the MMVF have the following levels of elements, calculated as oxides in wt%:
- the MMVF made by the method of the invention preferably have the composition in wt%: SiO 2 35 to 50 Al 2 O 3 12 to 30 TiO 2 up to 2 Fe 2 O 3 3 to 12 CaO 5 to 30 MgO up to 15 Na 2 O 0 to 15 K2O 0 to 15 P 2 O 5 up to 3 MnO up to 3 B 2 O 3 up to 3
- Another preferred composition for the MMVF is as follows in wt%:
- Glass fibres commonly comprise the following oxides, in percent by weight:
- Glass fibres can also contain the following oxides, in percent by weight:
- Some glass fibre compositions can contain Al 2 O 3 : less than 2%.
- the mineral fibres are hydrophobically treated mineral fibres, preferably hydrophobically treated stone wool.
- the hydrophobic treatment is a common treatment and may be effected e.g. by adding at least one hydrophobic agent such as a mineral oil, a siloxane or a silicon resinduring the mineral fibre manufacturing process, forming a hydrophobic film around the fibres.
- hydrophobically treated mineral fibres preferably have a hydrophobic film on the surface thereof.
- Suitable fibre formation methods and subsequent production steps for manufacturing the mineral fibre product are those conventional in the art.
- the binder is sprayed immediately after fibrillation of the mineral melt on to the airborne mineral fibres.
- the non-cured and preferably aqueous binder composition is normally applied in an amount of 0.1 to 18%, preferably 0.2 to 8 % by weight, of the bonded mineral fibre product on a dry basis.
- the spray-coated mineral fibre web is generally cured in a curing oven by means of a hot air stream.
- the hot air stream may be introduced into the mineral fibre web from below, or above or from alternating directions in distinctive zones in the length direction of the curing oven.
- the curing oven is operated at a temperature of from about 150°C to about 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.
- the curing oven residence time is from 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes, depending on, for instance, the product density.
- the mineral fibre product according to the present invention is cured at a temperature of 150°C to 250°C for a time of 30 seconds to 20 minutes.
- the mineral fibre web may be subjected to a shaping process before curing.
- the bonded mineral fibre product emerging from the curing oven may be cut to a desired format e.g., in the form of a batt.
- the mineral fibre product according to the present invention is a thermal and/or acoustic insulation product, preferably a thermal insulation product.
- the mineral fibre products can have the form of a preformed pipe section, a wired mat or a slab.
- the preformed pipe section may be a in the form of a hollow cylinder or a part thereof.
- the dimensions of the preformed pipe section shall fit to the pipe to be insulated.
- Wired mats are lightly bonded mineral fibre mats stitched on galvanized wired mesh with galvanized wire.
- the mineral fibre product according to the present invention is a thermal and/or acoustic insulation for a pipe, a storage tank, a boiler, a vessel or a column, preferably a pipe.
- the mineral fibre product according to the present invention has a thickness in the range of 20 mm to 500 mm or 25 mm to 300 mm, preferably 30 mm to 300 mm, such as 50 mm to 150 mm, wherein in general the mineral fibre product is in form of a sheet.
- the mineral fibre products according to the present invention generally have a density within the range of from 6 to 250 kg/m 3 , preferably 20 to 200 kg/m 3 .
- the mineral fibre products generally have a loss on ignition (LOI) within the range of 0.3 to 18.0 %, preferably 0.5 to 8.0 %.
- LOI loss on ignition
- a use according to the present invention of a mineral fibre product is directed to a use as a thermal and/or acoustic insulation, in particular as non-corrosive thermal and/or acoustic insulation.
- non-corrosive here means that the thermal and/or acoustical insulation material does not contribute to increased corrosion. "Non-corrosive” does not imply that corrosion cannot appear, but then it is caused by other factors than the thermal and/or acoustical insulation material itself.
- the invention also relates to a use of a mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation.
- the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- the mineral fibre product is used as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation, for an object selected from a pipe, a storage tank, a boiler, a vessel or a column, preferably a pipe.
- a pipe or pipework, respectively, also includes exhaust ducts.
- the mineral fibre product is used as a thermal and/or acoustic insulation for an object made of metal, wherein the object is generally a hollow object, for which examples are given above.
- the metal is preferably selected from copper or steel, wherein steel is preferred.
- the steel is preferably carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low alloy steel.
- the object is a steel pipe.
- the use is preferably at temperatures in the range of -20 °C to 320 °C, more preferably 0 °C to 200 °C, such as 50 °C to 175 °C.
- the temperature refers to the temperature of the object insulated by the mineral fibre product, i.e. the operating temperature.
- the operation may be continuous or cyclic with respect to the temperature. In case of cyclic operation, the above temperature range generally refers to the maximum temperature of the operation.
- the object covered by the mineral fibre product as a thermal and/or acoustic insulation in particular a non-corrosive thermal and/or acoustic insulation, generally includes a medium which may be selected from a gas, steam or a fluid.
- the mineral fibre product for the use according to the invention can have all features which have been described above for the inventive mineral fibre product so that reference is made thereto.
- the invention also relates to a hollow object covered with a mineral fibre product as a thermal and/or acoustic insulation, wherein the mineral fibre product comprises mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins.
- the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- the hollow object is selected from a pipe, a storage tank, a boiler, a vessel or a column, preferably a pipe.
- a pipe or pipework, respectively, also includes exhaust ducts.
- the hollow object is made of metal.
- the metal is preferably selected from copper or steel, wherein steel is preferred.
- the steel is preferably carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low alloy steel.
- the object is a steel pipe.
- the mineral fibre product covering the hollow object according to the invention can have all features which have been described above for the inventive mineral fibre product so that reference is made thereto.
- Oxidised lignins which can be used as component in the binder composition, preferably the aqueous binder composition, for mineral fibres according to the present invention and method for preparing such oxidised lignins
- oxidised lignins which can be used as component of the binder composition and their preparation.
- Oxidised lignins which can be used as component for the binders used in the present invention can be prepared by a method comprising bringing into contact
- Component (a) comprises one or more lignins.
- component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof.
- component (a) comprises one or more kraft lignins.
- component (b) comprises ammonia, one or more amino components, and/or any salts thereof.
- the present inventors have surprisingly found that the lignins oxidised by an oxidation agent in the presence of ammonia or amines contain significant amounts of nitrogen as a part of the structure of the oxidised lignins. Without wanting to be bound to any particular theory, the present inventors believe that the improved fire resistance properties of the oxidised lignins when used in products where they are comprised in a binder composition, said oxidised lignins prepared by the method according to the present invention, are at least partly due to the nitrogen content of the structure of the oxidised lignins.
- component (b) comprises ammonia and/or any salt thereof.
- the present inventors believe that the improved stability properties of the derivatized lignins prepared according to the present invention are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast to that, it has proven difficult to remove residual amounts of the alkali hydroxides used in the previously known oxidation process.
- component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
- component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof
- the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
- component (c) comprises one or more oxidation agents.
- component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
- active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained.
- the average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, the inventors have typically seen moderate increase of average molecular weight of around 30%.
- component (c) comprises hydrogen peroxide.
- Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to radical formation:
- the present inventors have found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidised lignins prepared in the process according to the present invention plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method according to the present invention.
- oxidised lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibers.
- the method according to the present invention comprises further components, in particular a component (d) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
- a component (d) in form of an oxidation catalyst such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
- Such oxidation catalysts can increase the rate of the reaction, thereby improving the properties of the oxidised lignins prepared by the method according to the present invention.
- the method comprises the steps of:
- the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH ⁇ 9, such as ⁇ 10, such as ⁇ 10.5.
- the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 10.5 to 12.
- the pH adjusting step is carried out so that the temperature is allowed to raise to ⁇ 25 °C and then controlled in the range of 25 - 50 °C, such as 30 - 45 °C, such as 35 - 40 °C.
- the temperature is allowed to raise ⁇ 35 °C and is then controlled in the range of 35 - 150 °C, such as 40 - 90 °C, such as 45 - 80 °C.
- the oxidation step is carried out for a time of 1 second to 48 hours, such as 10 seconds to 36 hours, such as 1 minute to 24 hours such as 2 - 5 hours.
- Oxidised lignins which can be used as component for the binders used in the present invention can be prepared by a method comprising bringing into contact
- Component (a) comprises one or more lignins.
- component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof.
- component (a) comprises one or more kraft lignins.
- component (b) comprises ammonia, one or more amino components, and/or any salts thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
- Ammonia-oxidized lignins is to be understood as a lignin that has been oxidized by an oxidation agent in the presence of ammonia.
- AOL ammonia-oxidized lignin
- component (b) comprises ammonia and/or any salt thereof.
- the present inventors believe that the improved stability properties of the derivatized lignins prepared according to the present invention with component (b) being ammonia and/or any salt thereof are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused.
- component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
- component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof
- the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
- component (c) comprises one or more oxidation agents.
- component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
- active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism, multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained.
- the average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, the inventors have typically seen moderate increase of average molecular weight of around 30%.
- component (c) comprises hydrogen peroxide.
- Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to radical formation:
- the present inventors have found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidized lignins prepared in the process according to the present invention plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method according to the present invention.
- oxidized lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibres.
- Component (d) comprises one or more plasticizers.
- component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea., or any mixtures thereof.
- polyols such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and
- component (d) in form of one or more plasticizers provides a decrease of the viscosity of the reaction mixture which allows a very efficient method to produce oxidised lignins.
- component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
- polyols such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
- component (d) comprises one or more plasticizers selected from the group of polyethylene glycols, polyvinyl alcohol, urea or any mixtures thereof.
- the method according to the present invention comprises further components, in particular a component (v) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
- a component (v) in form of an oxidation catalyst such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
- Such oxidation catalysts can increase the rate of the reaction, thereby improving the properties of the oxidized lignins prepared by the method.
- the method according to the present invention is carried out such that the method comprises
- the "dry weight of lignin" is preferably defined as the weight of the lignin in the supplied form.
- the method comprises the steps of:
- the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH ⁇ 9, such as ⁇ 10, such as ⁇ 10.5.
- the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 9.5 to 12.
- the pH adjusting step is carried out so that the temperature is allowed to raise to ⁇ 25 °C and then controlled in the range of 25 - 50 °C, such as 30 - 45 °C, such as 35 - 40 °C.
- the temperature is allowed to raise to ⁇ 35 °C and is then controlled in the range of 35 - 150 °C, such as 40 - 90 °C, such as 45 - 80 °C.
- the oxidation step is carried out for a time of 1 seconds to 24 hours, such as 1 minutes to 12 hours, such as 10 minutes to 8 hours, such as 5 minutes to 1 hour.
- the present inventors have found that the process according to the present invention allows to produce a high dry matter content of the reaction mixture and therefore a high throughput is possible in the process according to the present invention which allows the reaction product in form of the oxidised lignins to be used as a component in industrial mass production products such as mineral fibre products.
- the method according to the present invention is carried out such that the dry matter content of the reaction mixture is 20 to 80 wt.%, such as 40 to 70 wt.%.
- the method according to the present invention is carried out such that the viscosity of the oxidised lignin has a value of 100 cP to 100.000 cP, such as a value of 500 cP to 50.000 cP, such as a value of 1.000 cP to 25.000 cP.
- viscosity is dynamic viscosity and is defined as the resistance of the liquid/paste to a change in shape, or movement of neighbouring portions relative to one another.
- the viscosity is measured in centipoise (cP), which is the equivalent of 1 mPa s (milipascal second).
- Viscosity is measured at 20°C using a viscometer.
- the dynamic viscosity can be measured at 20°C by a Cone Plate Wells Brookfield Viscometer.
- the method according to the present invention is carried out such that the method comprises a rotator-stator device.
- the method according to the present invention is carried out such that the method is performed as a continuous or semi-continuous process.
- the present invention is also directed to an apparatus for performing the method described above.
- the apparatus for performing the method comprises:
- the apparatus is constructed in such a way that the inlets for the premix of the components (a), (b) and (d) are to the rotor-stator device and the apparatus furthermore comprises a chamber,
- a rotator-stator device is a device for processing materials comprising a stator configured as an inner cone provided with gear rings.
- the stator cooperates with a rotor having arms projecting from a hub. Each of these arms bears teeth meshing with the teeth of the gear rings of the stator. With each turn of the rotor, the material to be processed is transported farther outward by one stage, while being subjected to an intensive shear effect, mixing and redistribution.
- the rotor arm and the subjacent container chamber of the upright device allow for a permanent rearrangement of the material from the inside to the outside and provide for a multiple processing of dry and/or highly viscous matter so that the device is of excellent utility for the intensive mixing, kneading, fibrillating, disintegrating and similar processes important in industrial production.
- the upright arrangement of the housing facilitates the material's falling back from the periphery toward the center of the device.
- the rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator.
- the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow.
- a feed screw is provided that feeds towards the working region of the device.
- the guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
- the method is carried out such that the method uses one rotator-stator device.
- the mixing of the components and the reaction of the components is carried out in the same rotator-stator device.
- the method is carried out such that the method uses two or more rotator-stator devices, wherein at least one rotator-stator device is used for the mixing of the components and at least one rotator-stator device is used for reacting the components.
- This process can be divided into two steps:
- the highly concentrated (45 to 50 wt-%) mass of Lignin/water is prepared.
- the lignin powder is added slowly to the warm water (30 to 60 deg.C) in which the correct amount of watery ammonia and/or alkali base have been added. This can be done in batch mode, or the materials are added intermittently/continuously creating a continuous flow of mass to the next step.
- the created mass should be kept at a temperature of about 60 deg. to keep the viscosity as low as possible and hence the material pumpable.
- the hot mass of lignin/water at a pH of 9 to 12 is then transferred using a suitable pump, e.g. progressive cavity pump or another volumetric pump, to the oxidation step.
- the oxidation is done in a closed rotor-/stator system in a continuous inline reaction.
- a watery solution of ammonia and/or alkali base is dosed with a dosing pump into the rotor-/stator chamber at the point of highest turbulence/shear. This ensures a rapid oxidation reaction.
- the oxidized material (AOL) leaves the inline-reactor and is collected in suitable tanks.
- the present inventors have surprisingly found, that the oxidized lignins prepared have very desirable reactivity properties and at the same time display improved fire resistance properties when used in products where they are comprised in a binder composition, and improved long term stability over previously known oxidized lignins.
- the oxidised lignin also displays improved hydrophilicity.
- An important parameter for the reactivity of the oxidized lignins prepared is the carboxylic acid group content of the oxidized lignins.
- the oxidized lignin prepared has a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 2.0 mmol/g, such as 0.40 to 1.5 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (a).
- the oxidized lignin prepared has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (a), such as more than 2 groups, such as more than 2.5 groups.
- Oxidised lignins which can be used as a component for the binder used in the present invention can be prepared by a method comprising bringing into contact
- Components (a), (b), (c) and (d) are as defined above under Method II to prepare oxidised lignins.
- the process comprises a premixing step in which components are brought into contact with each other.
- the premixing step is carried out as a separate step and the mixing/oxidation step is carried out subsequently to the premixing step.
- component (c) is then added to the premixture produced in the premixing step.
- the premixing step corresponds to the mixing/oxidation step.
- the components for example component (a), component (b) and component (c) are mixed and an oxidation process is started at the same time. It is possible that the subsequent dwell time is performed in the same device as that used to perform the mixing/oxidation step.
- component (c) is air.
- the present inventors have found out that by allowing a mixing/oxidation step followed by an oxidation step, in which the reaction mixture is preferably not continued to be mixed, the oxidation rate can be controlled in a very efficient manner. At the same time, the costs for performing the method are reduced because the oxidation step subsequent to the mixing/oxidation step requires less complex equipment.
- oxidized lignin which is produced is particularly stable.
- the oxidized lignin produced is very well adjustable in terms of viscosity.
- concentration of the oxidized lignin can be very high.
- the dwell time is so chosen that the oxidation reaction is brought to the desired degree of completion, preferably to full completion.
- system for performing the method comprises:
- the system comprises one or more inlets for component (c) and/or component (d).
- the system comprises a premixing device.
- the premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
- the premixing device comprises inlets for water and component (a) and component (b).
- component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
- the system is constructed in such a way that
- the premixing step and the mixing/oxidizing step are carried out simultaneously.
- the premixing device and the mixing/oxidizing device are a single device, i. e. a rotor-stator device.
- one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator.
- the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow.
- a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
- system for performing the method comprises:
- the system comprises additional one or more inlets for component (c) and/or component (d).
- the system comprises a premixing device.
- the premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
- the premixing device comprises inlets for water and component (a) and component (b).
- component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
- the system is constructed in such a way that the inlets for components (a), (b) and (d) are inlets of an open rotor-stator device, whereby the system furthermore comprises a mixer/heat-exchanger, having an inlet for component (c) and an outlet for an oxidized lignin.
- premixing step and the mixing/oxidizing step are carried out simultaneously.
- the premixing device and the mixing/oxidizing device are a single device.
- one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator.
- the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow.
- a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
- premixing devices can also be used as premixing devices.
- the premixing step is carried out in the mixing and oxidizing apparatus.
- the mixing and oxidizing apparatus is a static mixer.
- a static mixer is a device for the continuous mixing of fluid materials, without moving components.
- One design of static mixer is the plate-type mixer and another common device type consists of mixer elements contained in a cylindrical (tube) or squared housing.
- the mixer/heat-exchanger is constructed as multitube heat exchanger with mixing elements.
- the mixing element are preferably fixed installations through which the mixture has to flow, whereby mixing is carried out as a result of the flowing through.
- the mixer/heat-exchanger can be constructed as a plug flow reactor.
- kraft lignin is soluble in water at relatively high pH, it is known that at certain weight percentage the viscosity of the solution will strongly increase. It is typically believed that the reason for the viscosity increase lies in a combination of strong hydrogen bonding and interactions of n-electrons of numerous aromatic rings present in lignin. For kraft lignin an abrupt increase in viscosity around 21-22 wt.-% in water was observed and 19 wt.-% of kraft lignin were used in the example presented.
- Ammonia aqueous solution was used as base in the pH adjusting step.
- the amount was fixed at 4 wt.-% based on the total reaction weight.
- the pH after the pH adjusting step and at the beginning of oxidation was 10.7.
- Table IA2 shows the results of CHNS elemental analysis before and after oxidation of kraft lignin. Before the analysis, the samples were heat treated at 160 °C to remove adsorbed ammonia. The analysis showed that a certain amount of nitrogen became a part of the structure of the oxidised lignin during the oxidation process.
- the oxidation is an exothermic reaction and increase in temperature is noted upon addition of peroxide.
- temperature was kept at 60 °C during three hours of reaction.
- V 2s and V 1s are endpoint volumes of a sample while V 2b and V 1b are the volume for the blank.
- C acid is 0.1M HCl in this case and m s is the weight of the sample.
- Table IA4 The values obtained from aqueous titration before and after oxidation are shown in table IA4.
- the average COOH functionality can also be quantified by a saponification value which represents the number of mg of KOH required to saponify 1 g lignin. Such a method can be found in AOCS Official Method Cd 3-25.
- Average molecular weight was also determined before and after oxidation with a PSS PolarSil column (9:1 (v/v) dimethyl sulphoxide/water eluent with 0.05 M LiBr) and UV detector at 280nm. Combination of COOH concentration and average molecular weight also allowed calculating average carboxylic acid group content per lignin macromolecule and these results are shown in table IA5.
- Example IB upscaling the lignin oxidation in ammonia by hydrogen peroxide to pilot scale
- the first scale up step was done from 1 L (lab scale) to 9 L using a professional mixer in stainless steel with very efficient mechanical mixing
- the next scale up step was done in a closed 200 L reactor with efficient water jacket and an efficient propeller stirrer.
- the scale was this time 180 L and hydrogen peroxide was added in two steps with appr. 30 minute separation.
- This up-scaling went relatively well, though quite some foaming was an issue partly due to the high degree reactor filling.
- To control the foaming a small amount of food grade defoamer was sprayed on to the foam. Most importantly the temperature controllable and end temperatures below 70 °C were obtained using external water-cooling.
- the pilot scale reactions were performed in an 800 L reactor with a water cooling jacket and a twin blade propeller stirring. 158 kg of lignin (UPM LignoBoost TM BioPiva 100) with a dry-matter content of 67 wt.-% was de-lumped and suspended in 224 kg of water and stirred to form a homogenous suspension. With continued stirring 103 kg of 25% ammonia in water was pumped into the reactor and stirred another 2 hours to from a dark viscous solution of lignin.
- UPM LignoBoost TM BioPiva 100 UPM LignoBoost TM BioPiva 100
- Mn and Mw average molar masses as determined by size exclusion chromatography expressed in g/mol together with average carboxylic acid group content per lignin macromolecule before and after oxidation sample Mn, g/mol Mw, g/mol average COOH functionality kraft lignin 1968 21105 0.9 ammonia oxidised kraft lignin 2503 34503 2.0
- the content of each of the components in a given oxidised lignin solution is based on the anhydrous mass of the components or as stated below.
- Kraft lignin was supplier by UPM as BioPiva100 TM as dry powder.
- NH 4 OH 25% was supplied by Sigma-Aldrich and used in supplied form.
- H 2 O 2 , 30% was supplied by Sigma-Aldrich and used in supplied form or by dilution with water.
- PEG 200 was supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such.
- PVA Mw 89.000-98.000, Mw 85.000-124.000, Mw 130.000, Mw 146.000-186.000
- Cas no 9002-89-5 were supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such.
- the content of the oxidised lignin after heating to 200 °C for 1h is termed "Dry solid matter" and stated as a percentage of remaining weight after the heating.
- Disc-shaped stone wool samples (diameter: 5 cm; height 1 cm) were cut out of stone wool and heat-treated at 580 °C for at least 30 minutes to remove all organics.
- the solids of the binder mixture were measured by distributing a sample of the binder mixture (approx. 2 g) onto a heat treated stone wool disc in a tin foil container. The weight of the tin foil container containing the stone wool disc was weighed before and directly after addition of the binder mixture. Two such binder mixture loaded stone wool discs in tin foil containers were produced and they were then heated at 200 °C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the dry solids matter was calculated as an average of the two results.
- V 2s and V 1s are endpoint volumes of a sample while V 2b and V 1b are the volume for a blank sample.
- C acid is 0.1M HCl in this case and m s,g is the weight of the sample.
- entry numbers of the oxidised lignin example correspond to the entry numbers used in Table II.
- 71,0 g lignin UPM Biopiva 100 was dissolved in 149,0 g water at 20°C and added 13,3 g 25% NH 4 OH and stirred for 1h by magnetic stirrer, where after 16,8g H 2 O 2 30% was added slowly during agitation. The temperature was increased to 60°C in the water bath. After 1h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
- 71,0 g lignin UPM Biopiva 100 was dissolved in 57,1 g water at 20°C and added 13,3 g 25% NH 4 OH and stirred for 1h by mechanical stirrer, where after 16,6 g H 2 O 2 30% was added slowly during agitation. The temperature was increased to 60°C in the water bath. After 1h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
- This premix was then transferred to a rotor-stator device and a reaction device where the oxidation was made by use of H 2 O 2 (17,5 vol%).
- the reaction device used in this case has at least partially a reaction tube and a reaction vessel. Dosage of the premixture was 150 l/h and the H 2 O 2 was dosed at 18 l/h.
- a Cavitron CD1000 rotor-stator device was used to carry out the mixing/oxidation step.
- the rotor-stator device was run at 250 Hz (55 m/s circumferential speed) with a counter pressure at 2 bar.
- the dwell time in the reaction tube was 3,2 minutes and in the reaction vessel 2 hours.
- This premixture was then transferred to a static mixer and a mixer/heat-exchanger, where the oxidation was made by use of H 2 O 2 (35 vol%). Dosage of the premixture was 600 l/h and the H 2 O 2 was dosed at 17,2 l/h. The dwell time in the mixer/heat-exchanger was 20 minutes.
- the temperature of the mixture increased during the oxidation step up to 95 °C.
- the final product was analysed for the COOH group content, dry solid matter, pH, viscosity and remaining H 2 O 2 .
- a binder was made based on this AOL: 49,3 g AOL (19,0 % solids), 0,8 g primid XL552 (100 % solids) and 2,4 g PEG200 (100 % solids) were mixed with 0,8 g water to yield 19% solids; and then used for test of mechanical properties in bar tests.
- the mechanical strength of the binders was tested in a bar test. For each binder, 16 bars were manufactured from a mixture of the binder and stone wool shots from the stone wool spinning production.
- the water leachable chloride content of the mineral fibre product is measured according to EN 13468:2001.
- the standard specifies the equipment and procedures for determining trace quantities of the water soluble chloride in an aqueous extract of the product. Reference is made thereto.
- the water leachable chloride content is given in mg chloride per kg mineral fibre product.
- the quantity of organic material (loss of ignition) is determined as the loss of weight of the specimen obtained by burning away of organic material. This is done as specified in EN 13820.
- the binder content is taken as the LOI.
- the binder includes oil and other binder additives, if present.
- binder solids The content of binder after curing is termed "binder solids”.
- Disc-shaped stone wool samples (diameter: 5 cm; height 1 cm) were cut out of stone wool and heat-treated at 580 °C for at least 30 minutes to remove all organics.
- the solids of the binder mixture was measured by distributing a sample of the binder mixture (approx. 2 g) onto a heat treated stone wool disc in a tin foil container. The weight of the tin foil container containing the stone wool disc was weighed before and directly after addition of the binder mixture. Two such binder mixture loaded stone wool discs in tin foil containers were produced and they were then heated at 200 °C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the binder solids was calculated as an average of the two results.
- a foam dampening agent (Skumdaemper 11-10 from NCA-Verodan) is added. Temperature of the batch is maintained at 40°C.
- the temperature in the reaction mixture is controlled by heating or cooling in such a way that a final reaction temperature of 65°C is reached.
- AOL resin a binder was formulated by addition of 270 kg polyethylene glycol 200 (PEG 200) and 433 kg of a 31% solution of Primid XL-552 in water.
- Binder example reference binder A1, A2 and A5 (Phenol-formaldehyde resin modified with urea and dextrose, a PUF-resol)
- This binder is a phenol-formaldehyde resin modified with urea, a PUF-resol.
- a phenol-formaldehyde resin is prepared by reacting 37% aq. formaldehyde (606 g) and phenol (189 g) in the presence of 46% aq. potassium hydroxide (25.5 g) at a reaction temperature of 84°C preceded by a heating rate of approximately 1°C per minute. The reaction is continued at 84 °C until the acid tolerance of the resin is 4 and most of the phenol is converted. Urea (241 g) is then added and the mixture is cooled.
- the acid tolerance expresses the number of times a given volume of a binder can be diluted with acid without the mixture becoming cloudy (the binder precipitates). Sulfuric acid is used to determine the stop criterion in a binder production and an acid tolerance lower than 4 indicates the end of the binder reaction.
- a titrant is produced from diluting 2.5 ml conc. sulfuric acid (>99 %) with 1 L ion exchanged water. 5 mL of the binder to be investigated is then titrated at room temperature with this titrant while keeping the binder in motion by manually shaking it; if preferred, use a magnetic stirrer and a magnetic stick. Titration is continued until a slight cloud appears in the binder, which does not disappear when the binder is shaken.
- AT Used titration volume mL / Sample volume mL
- a binder is made by addition of 25% aq. ammonia (90 mL) and ammonium sulfate (13.2 g) followed by water (1.30 kg).
- Binder example A3 and A4 are Binder example A3 and A4:
- example A1 Made as described in example A1, but without addition of dextrose.
- binder example A3 process water is used, and for A4 osmosis water.
- Binder example reference binder B
- a foam dampening agent (Skumdaemper 11-10 from NCA-Verodan) is added. Temperature of the batch is maintained at 40°C.
- the temperature in the reaction mixture is controlled by heating or cooling in such a way that a final reaction temperature of 65°C is reached.
- the AOL used was prepared as described in the paragraph above using the amount of raw materials as specified in table 1.
- the AOL resin was mixed to binders by use of the raw materials specified in table 1.
- Stonewool products with Reference binders A1 to A5, B (reference products) and binders 1 to 6 (inventive products) were made in a standard stonewool factory using the specified water type in table 1.
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Description
- The present invention relates to a mineral fibre product, and a use of a mineral fibre product.
- Mineral fibre products (also termed mineral wool products) generally comprise mineral fibres (also termed as man-made vitreous fibres (MMVF)) such as, e.g., glass fibres, ceramic fibres, basalt fibres, slag fibres, and stone fibres (rock fibres), which are bonded together by a cured thermoset polymeric binder material. For use as thermal or acoustical insulation products, bonded mineral fibre mats are generally produced by converting a melt made of suitable raw materials to fibres in conventional manner, for instance by a spinning cup process or by a cascade rotor process. The fibres are blown into a forming chamber and, while airborne and while still hot, are sprayed with a binder solution and randomly deposited as a mat or web onto a travelling conveyor. The fibre mat is then transferred to a curing oven where heated air is blown through the mat to cure the binder and rigidly bond the mineral fibres together.
- In the past, the binder resins of choice have been phenol-formaldehyde resins which can be economically produced and can be extended with urea prior to use as a binder. However, the existing and proposed legislation directed to the lowering or elimination of formaldehyde emissions have led to the development of formaldehyde-free binders such as, for instance, the binder compositions based on polycarboxy polymers and polyols or polyamines, such as disclosed in
EP-A-583086 EP-A-990727 EP-A-1741726 ,US-A-5,318,990 andUS-A-2007/0173588 . - Another group of non-phenol-formaldehyde binders are the addition/-elimination reaction products of aliphatic and/or aromatic anhydrides with alkanolamines, e.g., as disclosed in
WO 99/36368 WO 01/05725 WO 01/96460 WO 02/06178 WO 2004/007615 andWO 2006/061249 . These binder compositions are water soluble and exhibit excellent binding properties in terms of curing speed and curing density.WO 2008/023032 discloses urea-modified binders of that type which provide mineral wool products having reduced moisture take-up.WO 2016/120576 describes ammonium lighosulphonates as binder andFR-2976584 - Since some of the starting materials used in the production of these binders are rather expensive chemicals, there is an ongoing need to provide formaldehyde-free binders which are economically produced.
- A further effect in connection with previously known aqueous binder compositions from mineral fibres is that at least the majority of the starting materials used for the productions of these binders stem from fossil fuels. There is an ongoing trend of consumers to prefer products that are fully or at least partly produced from renewable materials and there is therefore a need to provide binders for mineral wool which are, at least partly, produced from renewable materials.
- A major problem of the use of mineral fibre products as thermal or acoustical insulation for industrial equipment or piping is corrosion. Thus, Corrosion Under Insulation (CUI) refers to the external corrosion of piping or equipment that occurs underneath externally cladded insulation due to water or moisture penetration. The corroded surface is mostly hidden by the insulation system and will not be observed until the insulation is removed for inspection or in the event of metal failure and/or leakage leading to health and safety incidents. CUI occurs in particular under insulation for steel structures which undergo cyclic temperature changes like e.g. pipelines in the oil and gas industry.
- Corrosion occurs in the presence of water and oxygen. If the equipment or piping such as steelwork under insulation remains dry there is no corrosion problem. However, keeping insulation dry can be difficult. A certain type of corrosion can be caused or supported by water-soluble chlorides. Prior art binder compositions for mineral fibres can include significant amounts of water-soluble chlorides. Accordingly, the mineral fibre product itself can contribute to the corrosion of the insulated parts.
- The risk of corrosion under insulation of carbon steel is considered high in the temperature range of 50 to 175°C and extreme in cyclic temperature service between -20 and 320°C. The most frequently occurring types of CUI are general and pitting corrosion of carbon steel which may occur if wet insulation comes in contact with carbon steel, and external stress corrosion tracking (ESCT) of austenitic stainless steel, which is a specific type of corrosion mainly caused by the action of water-soluble chloride
- Accordingly, it was an object of the present invention to provide a mineral fibre product for insulation which has a reduced corrosiveness towards the insulated objects, is economically produced and is using renewable materials as starting products for the preparation of the aqueous binder composition used to produce the mineral fibre product.
- A further object of the present invention was to provide a use of such mineral fibre product.
- In accordance with a first aspect of the present invention, there is provided a mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- In accordance with a second aspect of the present invention, there is provided a use of a mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- In accordance with a third aspect of the present invention, there is provided a method for the manufacture of a mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001,
the method comprising the steps of - a) providing a non-cured aqueous binder composition comprising one or more oxidized lignins and water,
- b) contacting mineral fibres with the non-cured aqueous binder composition, and
- c) curing the binder composition in contact with the mineral fibers,
- In accordance with a forth aspect of the present invention, there is provided a hollow object covered with a mineral fibre product as a thermal and/or acoustic insulation, wherein the mineral fibre product comprises mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- The inventors have found that it is possible to use a mineral fibre product as a low corrosive or even non-corrosive thermal and/or acoustic insulation, when a binder composition based on oxidized lignin is used for the mineral fibre product. This binder composition has a surprisingly low water leachable chloride content.
- The mineral fibre product of the invention comprises mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001, wherein the water leachable chloride content is preferably less than 6 mg/kg in accordance with EN 13468:2001.
- For the purpose of the present application, the water leachable chloride content of the mineral fibre product is measured according to EN 13468:2001. The standard EN 13468:2001 inter alia relates to the determination of trace quantities of water soluble chloride in thermal insulating products for building equipment and industrial installations. The standard specifies the equipment and procedures for determining trace quantities of the water soluble chloride in an aqueous extract of the product. Reference is made to this standard for the details.
- The water leachable chloride content is given in mg chloride per kg mineral fibre product. Referring to table 1 in the EN standard, 100°C and 0,5h for leaching is used. Sample preparation according to 7.2.1 of EN 13468. Analysis according to 7.2.2.2 of EN 13468 (ion chromatography determination).
- The inventors found that the mineral fibre products of the present invention have a surprisingly low water leachable chloride content. This is even true when non-purified water such as tap water or process water is used for preparing the non-cured binder composition. As known by the skilled person, non-purified water can contain considerable amounts of chloride.
- Without wanting to be bound by any particular theory, the present inventors believe that that the low water leachable chloride content of the mineral fibre products of the invention, even if tap water or process water is used for preparing the binder composition, is at least partly based on a capture of chloride ions within the binder matrix based on oxidized lignin. This capture foreclose leaching of the chloride so that it is not available for corrosive activity.
- In general, the uncured binder composition is an aqueous binder composition. The water contained in the aqueous binder composition may be purified water, non-purified water or a combination of purified water and non-purified water added.
- In a preferred embodiment, the non-cured binder composition is an aqueous binder composition, wherein at least part of the water or the total water contained in the aqueous binder composition is non-purified water, the other part of the water, if any, being purified water. This is surprising since in common prior art binders purified water is usually used to avoid considerable chloride contents. Examples of purified water are osmosis water, deionized water or distilled water and further are mentioned below.
- Purified water is generally water that has been mechanically filtered or processed to remove impurities and make it suitable for use. Distilled water has been the most common form of purified water, but, in recent years, water is more frequently purified by other processes including capacitive deionization, reverse osmosis, carbon filtering, microfiltration, ultrafiltration, ultraviolet oxidation, or electrodeionization. It is preferred that the purified water used in the non-cured binder composition has a chloride content of less than 10 mg/L, preferably less than 5 mg/L.
- Examples of suitable non-purified water is tap water, rain water, process water or a combination thereof. The chloride content of tap water and rain water is generally in the range of 10-200 mg/L. The chloride content of process water is generally in the range of 25-200 mg/L chloride. It is preferred that the non-purified water used in the non-cured binder composition can have a chloride content of at least 10 mg/L, such as a chloride content in the range of 10-200 mg/L.
- The proportion of non-purified water added can be in the range of 0 to 100 wt.-%, preferably 30 to 100 wt.-%, most preferred 50 to 100 wt.-%, based on the total weight of water contained in the non-cured binder composition, the other proportion, if any, being purified water.
- In a production plant, the binder composition is usually produced in a concentrated form, i.e. the water content is kept low. After delivery, the concentrated binder composition is diluted by addition of water on site of the mineral fibre production to a suitable viscosity. The diluted binder composition is contacted with the mineral fibres and is cured to produce the mineral fibre product. It is a benefit of the present invention that non-purified water such as tap water, rain water or process water can be used for diluting the concentrated binder composition and nevertheless products with low water leachable chloride content are achieved.
- In a preferred embodiment, the binders according to the present invention are formaldehyde free.
- For the purpose of the present application, the term "formaldehyde free" is defined to characterize a mineral wool product where the emission is below 5 µg/m2/h of formaldehyde from the mineral wool product, preferably below 3 µg/m2/h. Preferably, the test is carried out in accordance with ISO 16000 for testing aldehyde emissions.
- The non-cured binder composition for preparing of the mineral fibre product according to the present invention comprises one or more oxidized lignins as a component (i).
- Component (i) is in form of one or more oxidized lignins.
- Lignin, cellulose and hemicellulose are the three main organic compounds in a plant cell wall. Lignin can be thought of as the glue, that holds the cellulose fibres together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, second only to cellulose, and is estimated to represent as much as 20-30% of the total carbon contained in the biomass, which is more than 1 billion tons globally.
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Fig. 1 shows a section from a possible lignin structure. - There are at least four groups of technical lignins available in the market. These four groups are shown in
Fig. 3 . A possible fifth group, Biorefinery lignin, is a bit different as it is not described by the extraction process, but instead by the process origin, e.g. biorefining and it can thus be similar or different to any of the other groups mentioned. Each group is different from each other and each is suitable for different applications. Lignin is a complex, heterogenous material composed of up to three different phenyl propane monomers, depending on the source. Softwood lignins are made mostly with units of coniferyl alcohol, seefig. 2 and as a result, they are more homogeneous than hardwood lignins, which has a higher content of syringyl alcohol, seefig. 2 . The appearance and consistency of lignin are quite variable and highly contingent on process. - A summary of the properties of these technical lignins is shown in
Fig. 4 . - Lignosulfonate from the sulfite pulping process remains the largest commercial available source of lignin, with capacity of 1.4 million tonnes. But taking these aside, the kraft process is currently the most used pulping process and is gradually replacing the sulfite process. An estimated 78 million tonnes per year of lignin are globally generated by kraft pulp production but most of it is burned for steam and energy. Current capacity for kraft recovery is estimated at 160,000 tonnes, but sources indicate that current recovery is only about 75,000 tonnes. Kraft lignin is developed from black liquour, the spent liquor from the sulfate or kraft process. At the moment, 3 well-known processes are used to produce the kraft lignin: LignoBoost, LignoForce and SLRP. These 3 processes are similar in that they involve the addition of CO2 to reduce the pH to 9-10, followed by acidification to reduce pH further to approximately 2. The final step involves some combination of washing, leaching and filtration to remove ash and other contaminants. The three processes are in various stages of commercialization globally.
- The kraft process introduces thiol groups, stilbene while some carbohydrates remain. Sodium sulphate is also present as an impurity due to precipitation of lignin from liquor with sulphuric acid but can potentially be avoided by altering the way lignin is isolated. The kraft process leads to high amount of phenolic hydroxyl groups and this lignin is soluble in water when these groups are ionized (above pH∼10).
- Commercial kraft lignin is generally higher in purity than lignosulfonates. The molecular weight are 1000-3000 g/mol.s
- Soda lignin originates from sodium hydroxide pulping processes, which are mainly used for wheat straw, bagasse and flax. Soda lignin properties are similar to kraft lignins one in terms of solubility and Tg. This process does not utilize sulphur and there is no covalently bound sulphur. The ash level is very low. Soda lignin has a low solubility in neutral and acid media but is completely soluble at pH 12 and higher.
- The lignosulfonate process introduces large amount of sulphonate groups making the lignin soluble in water but also in acidic water solutions. Lignosulfonates has up to 8% sulfur as sulphonate, whereas kraft lignin has 1-2% sulfur, mostly bonded to the lignin. The molecular weight of lignosulfonate is 15.000-50.000 g/mol. This lignin contains more leftover carbohydrates compared to other types and has a higher average molecular weight. The typical hydrophobic core of lignin together with large number of ionized sulphonate groups make this lignin attractive as a surfactant and it often finds application in dispersing cement etc.
- A further group of lignins becoming available is lignins resulting from biorefining processes in which the carbohydrates are separated from the lignin by chemical or biochemical processes to produce a carbohydrate rich fraction. This remaining lignin is referred to as biorefinery lignin. Biorefineries focus on producing energy, and producing substitutes for products obtained from fossil fuels and petrochemicals as well as lignin. The lignin from this process is in general considered a low value product or even a waste product mainly used for thermal combustion or used as low grade fodder or otherwise disposed of.
- Organosolv lignin availability is still considered on the pilot scale. The process involves extraction of lignin by using water together with various organic solvents (most often ethanol) and some organic acids. An advantage of this process is the higher purity of the obtained lignin but at a much higher cost compared to other technical lignins and with the solubility in organic solvents and not in water.
- Previous attempts to use lignin as a basic compound for binder compositions for mineral fibres failed because it proved difficult to find suitable cross-linkers which would achieve desirable mechanical properties of the cured mineral wool product and at the same time avoid harmful and/or corrosive components. Presently lignin is used to replace oil derived chemicals, such as phenol in phenolic resins in binder applications or in bitumen. It is also used as cement and concrete additives and in some aspects as dispersants.
- The cross-linking of a polymer in general should provide improved properties like mechanical, chemical and thermal resistance etc. Lignin is especially abundant in phenolic and aliphatic hydroxyl groups that can be reacted leading to cross-linked structure of lignin. Different lignins will also have other functional groups available that can potentially be used. The existence of these other groups is largely dependent on the way lignin was separated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in lignosulfonate etc.) depending on the source.
- It has been found that by using oxidized lignins, binder compositions for mineral fibres can be prepared which allow excellent properties of the mineral fibre product produced.
- In one embodiment, the component (i) is in form of one or more oxidized kraft lignins.
- In one embodiment, the component (i) is in form of one or more oxidized soda lignins.
- In one embodiment, the component (i) is in form of one or more ammonia-oxidized lignins. For the purpose of the present invention, the term "ammonia-oxidized lignins" is to be understood as a lignin that has been oxidized by an oxidation agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.
- In an alternative embodiment, the ammonia is partially or fully replaced by an alkali metal hydroxide, in particular sodium hydroxide and/or potassium hydroxide.
- A typical oxidation agent used for preparing the oxidized lignins is hydrogen peroxide.
- In one embodiment, the ammonia-oxidized lignin comprises one or more of the compounds selected from the group of ammonia, amines, hydroxides or any salts thereof.
- In one embodiment, the component (i) is having a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i).
- In the binder composition, preferably the aqueous binder composition, used according to the present invention, component (i), i.e. the one or more oxidized lignins, may be present in an amount of 25 to 95 wt.-%, such as 30 to 90 wt.-%, such as 35 to 85 wt.-%, based on the dry weight of the binder composition.
- In one embodiment, the component (i) is having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups.
- It is believed that the carboxylic acid group content of the oxidized lignins plays an important role in the surprising advantages of the binder compositions, preferably the aqueous binder compositions, for mineral fibres according to the present invention. In particular, it is believed that the carboxylic acid group of the oxidized lignins improve the cross-linking properties and therefore allow better mechanical properties of the cured mineral fibre products.
- In a preferred embodiment, the uncured binder composition, which is preferably an aqueous binder composition, for preparing the mineral fibre product according to the present invention comprises
- a component (i) in form of one or more oxidized lignins;
- a component (ii) in form of one or more cross-linkers;
- optionally a component (iii) in form of one or more plasticizers.
- Optional component (ii) is in form of one or more cross-linkers.
- In one embodiment, the component (ii) comprises in one embodiment one or more cross-linkers selected from β-hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers.
- β-hydroxyalkylamide-cross-linkers is a curing agent for the acid-functional macromolecules. It provides a hard, durable, corrosion resistant and solvent resistant cross-linked polymer network. It is believed the β-hydroxyalkylamide cross-linkers cure through esterification reaction to form multiple ester linkages. The hydroxy functionality of the β-hydroxyalkylamide-cross-linkers should be an average of at least 2, preferably greater than 2 and more preferably 2-4 in order to obtain optimum curing response.
- Oxazoline group containing cross-linkers are polymers containing one of more oxazoline groups in each molecule and generally, oxazoline containing crosslinkers can easily be obtained by polymerizing an oxazoline derivative. The patent
US6818699 B2 provides a disclosure for such a process. - In one embodiment, the component (ii) is an epoxidised oil based on fatty acid triglyceride.
- It is noted that epoxidised oils based on fatty acid triglycerides are not considered hazardous and therefore the use of these compounds in the binder compositions according to the present invention do not render these compositions unsafe to handle.
- In one embodiment, the component (ii) is a molecule having 3 or more epoxy groups.
- In one embodiment, the component (ii) is one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
- In one embodiment, component (ii) is selected from the group consisting of cross-linkers taking part in a curing reaction, such as hydroxyalkylamide, alkanolamine, a reaction product of an alkanolamine and a polycarboxylic acid. The reaction product of an alkanolamine and a polycarboxylic acid can be found in
US6706853B1 . - Without wanting to be bound by any particular theory, it is believed that the very advantageous properties of the binder compositions, preferably the aqueous binder compositions, used according to the present invention are due to the interaction of the oxidized lignins used as component (i) and the cross-linkers mentioned above. It is believed that the presence of carboxylic acid groups in the oxidized lignins enable the very effective cross-linking of the oxidized lignins.
- In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of multifunctional organic amines such as an alkanolamine, diamines, such as hexamethyldiamine, triamines.
- In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
- In one embodiment, the component (ii) is one or more fatty amides.
- In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of dimethoxyethanal, glycolaldehyde, glyoxalic acid.
- In one embodiment, the component (ii) is one or more cross-linkers selected from polyester polyols, such as polycaprolactone.
- In one embodiment, the component (ii) is one or more cross-linkers selected from the group consisting of starch, modified starch, CMC.
- In one embodiment, the component (ii) is one or more cross-linkers in form of aliphatic multifunctional carbodiimides;
- In one embodiment, the component (ii) is one or more cross-linkers selected from melamine based cross-linkers, such as a hexakis(methylmethoxy)melamine (HMMM) based cross-linkers.
- Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), such as ZOLDINE® XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).
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- Component (ii) can also be any mixture of the above mentioned compounds.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises component (ii) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of component (i).
- Optional component (iii) is in form of one or more plasticizers.
- In one embodiment, component (iii) is in form of one or more plasticizers selected from the group consisting of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
- In one embodiment, component (iii) is in form of one or more plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin like vanillin, acetosyringone, solvents used as coalescing agents like alcohol ethers, polyvinyl alcohol.
- In one embodiment, component (iii) is in form of one or more non-reactive plasticizer selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or other esters, solvents used as coalescing agents like alcohol ethers, acrylic polymers, polyvinyl alcohol.
- In one embodiment, component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and/or vanillic acid and/or ferullic acid, polyurethane dispersions, acrylic based polymers with free carboxy groups, compounds with a structure similar to lignin like vanillin, acetosyringone.
- In one embodiment, component (iii) is in form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.
- In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers.
- Another particular surprising aspect of the present invention is that the use of plasticizers having a boiling point of more than 100 °C, in particular 140 to 250 °C, strongly improves the mechanical properties of the mineral fibre products according to the present invention although, in view of their boiling point, it is likely that these plasticizers will at least in part evaporate during the curing of the binders, preferably the aqueous binders, in contact with the mineral fibres.
- In one embodiment, component (iii) comprises one or more plasticizers having a boiling point of more than 100 °C, such as 110 to 280 °C, more preferred 120 to 260 °C, more preferred 140 to 250 °C.
- It is believed that the effectiveness of these plasticizers in the binder composition, preferably the aqueous binder composition, used according to the present invention is associated with the effect of increasing the mobility of the oxidized lignins during the curing process. It is believed that the increased mobility of the lignins or oxidized lignins during the curing process facilitates the effective cross-linking.
- In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50000 g/mol, in particular 150 to 4000 g/mol, more particular 150 to 1000 g/mol, preferably 150 to 500 g/mol, more preferably 200 to 400 g/mol.
- In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g/mol, in particular 4000 to 15000 g/mol, more particular 8000 to 12000 g/mol.
- In one embodiment component (iii) is capable of forming covalent bonds with component (i) and/or component (ii) during the curing process. Such a component would not evaporate and remain as part of the composition but will be effectively altered to not introduce unwanted side effects e.g. water absorption in the cured product. Non-limiting examples of such a component are caprolactone and acrylic based polymers with free carboxyl groups.
- In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydroxy alcohols, such as pentanol, stearyl alcohol.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxylates such as ethoxylates such as butanol ethoxylates, such as butoxytriglycol.
- In one embodiment, component (iii) is selected from one or more propylene glycols.
- In one embodiment, component (iii) is selected from one or more glycol esters.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives such as alkyl or aryl substituted phenols.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates; such as tributylphosphates.
- In one embodiment, component (iii) is selected from one or more hydroxy acids.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides such as acetamides, benzamide, fatty acid amides such as tall oil amides.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyldimethylammoniumchloride.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil.
- In one embodiment, component (iii) is in form of tall oil.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.
- In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.
- In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucoseamides, sucrose esters, sorbitan esters.
- It has surprisingly been found that the inclusion of plasticizers in the binder composition, preferably the aqueous binder composition, used according to the present invention strongly improves the mechanical properties of the mineral fibre products according to the present invention.
- The term plasticizer refers to a substance that is added to a material in order to make the material softer, more flexible (by decreasing the glass-transition temperature Tg) and easier to process.
- Component (iii) can also be any mixture of the above mentioned compounds.
- In one embodiment, component (iii) is present in an amount of 0.5 to 50, preferably 2.5 to 25, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).
- Binder composition, preferably aqueous binder composition for mineral fibers comprising components (i) and (iia)
- In one embodiment the present invention is directed to a binder composition, preferably an aqueous binder composition, for mineral fibers comprising:
- a component (i) in form of one or more oxidized lignins;
- a component (iia) in form of one or more modifiers.
- The present inventors have found that the excellent binder properties can also be achieved by a two-component system which comprises component (i) in form of one or more oxidized lignins and a component (iia) in form of one or more modifiers, and optionally any of the other components mentioned above and below.
- In one embodiment, component (iia) is a modifier in form of one or more compounds selected from the group consisting of epoxidised oils based on fatty acid triglycerides.
- In one embodiment, component (iia) is a modifier in form of one or more compounds selected from molecules having 3 or more epoxy groups.
- In one embodiment, component (iia) is a modifier in form of one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
- In one embodiment, component (iia) is one or more modifiers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
- In one embodiment, the component (iia) is one or more modifiers selected from aliphatic multifunctional carbodiimides.
- Component (iia) can also be any mixture of the above mentioned compounds.
- Without wanting to be bound by any particular theory, the present inventors believe that the excellent binder properties achieved by the binder composition for mineral fibers comprising components (i) and (iia), and optional further components, are at least partly due to the effect that the modifiers used as components (iia) at least partly serve the function of a plasticizer and a crosslinker.
- In one embodiment, the binder composition, preferably the aqueous binder composition, comprises component (iia) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of the component (i).
- In some embodiments, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises further components.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid, and/or any salts thereof such as sodium hypophosphite, and/or ammonium salts, such as ammonium salts of sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid, and/or sodium polyphosphate (STTP), and/or sodium metaphosphate (STMP), and/or phosphorous oxychloride. The presence of such a catalyst can improve the curing properties of the binder compositions, preferably the aqueous binder compositions, used according to the present invention.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F17)2]4.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from metal chlorides, such as KCI, MgCl2, ZnCl2, FeCl3 and SnCl2.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from organometallic compounds, such as titanate-based catalysts and stannum based catalysts.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention further comprises a further component (iv) in form of one or more silanes.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises a further component (iv) in form of one or more coupling agents, such as organofunctional silanes.
- In one embodiment, component (iv) is selected from group consisting of organofunctional silanes, such as primary or secondary amino functionalized silanes, epoxy functionalized silanes, such as polymeric or oligomeric epoxy functionalized silanes, methacrylate functionalized silanes, alkyl and aryl functionalized silanes, urea funtionalised silanes or vinyl functionalized silanes.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention further comprises a component (v) in form of one or more components selected from the group of ammonia, amines or any salts thereof.
- It has been found that the inclusion of ammonia, amines or any salts thereof as a further component can in particular be useful when oxidized lignins are used in component (i), which oxidised lignin have not been oxidized in the presence of ammonia.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention further comprises a further component in form of urea, in particular in an amount of 5 to 40 wt.-%, such as 10 to 30 wt.-%, 15 to 25 wt.-%, based on the dry weight of component (i).
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention further comprises a further component in form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, in particular dextrose, polycarbohydrates, and mixtures thereof, preferably dextrins and maltodextrins, more preferably glucose syrups, and more preferably glucose syrups with a dextrose equivalent value of DE = 30 to less than 100, such as DE = 60 to less than 100, such as DE = 60-99, such as DE = 85-99, such as DE = 95-99.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention further comprises a further component in form of one or more carbohydrates selected from the group consisting of sucrose and reducing sugars in an amount of 5 to 50 wt.-%, such as 5 to less than 50 wt.-%, such as 10 to 40 wt.-%, such as 15 to 30 wt.-% based on the dry weight of component (i).
- In the context of the present invention, a binder composition having a sugar content of 50 wt.-% or more, based on the total dry weight of the binder components, is considered to be a sugar based binder. In the context of the present invention, a binder composition having a sugar content of less than 50 wt.-%, based on the total dry weight of the binder components, is considered a non-sugar based binder.
- In one embodiment, the binder composition, preferably the aqueous adhesive composition, used according to the present invention further comprises a further component in form of one or more surface active agents that are in the form of non-ionic and/or ionic emulsifiers such as polyoxyethylenes (4) lauryl ether, such as soy lecithin, such as sodium dodecyl sulfate.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises
- a component (i) in form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i);
- a component (ii) in form of one or more cross-linkers selected from β-hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers and/or is one or more cross-linkers selected from the group consisting of multifunctional organic amines such as an alkanolamine, diamines, such as hexamethyldiamine, triamines;
- a component (iii) in form of one or more polyethylene glycols having an average molecular weight of 150 to 50000 g/mol, in particular 150 to 4000 g/mol, more particular 150 to 1000 g/mol, preferably 150 to 500 g/mol, more preferably 150 to 300 g/mol, or one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g/mol, in particular 4000 to 15000 g/mol, more particular 8000 to 12000 g/mol; wherein preferably the binder composition, preferably the aqueous binder composition, comprises component (ii) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, 6 to 12 wt.-%, based on the dry weight of component (i), and (iii) is present in an amount of 0.5 to 50, preferably 2.5 to 25, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises
- a component (i) in form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i);
- a component (iia) in form of one or more modifiers selected from epoxidised oils based on fatty acid triglycerides.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises
- a component (i) in form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups;
- a component (ii) in form of one or more cross-linkers selected from β-hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers and/or is one or more cross-linkers selected from the group consisting of multifunctional organic amines such as an alkanolamine, diamines, such as hexamethyldiamine, triamines;
- a component (iii) in form of one or more polyethylene glycols having an average molecular weight of 150 to 50000 g/mol, in particular 150 to 4000 g/mol, more particular 150 to 1000 g/mol, preferably 150 to 500 g/mol, more preferably 150 to 300 g/mol, or one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g/mol, in particular 4000 to 15000 g/mol, more particular 8000 to 12000 g/mol; wherein preferably the binder composition, preferably the aqueous binder composition, comprises component (ii) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, 6 to 12 wt.-%, based on the dry weight of component (i), and (iii) is present in an amount of 0.5 to 50, preferably 2.5 to 25, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention comprises
- a component (i) in form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups;
- a component (iia) in form of one or more modifiers selected from epoxidised oils based on fatty acid triglycerides.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention consists essentially of
- a component (i) in form of one or more oxidized lignins;
- a component (ii) in form of one or more cross-linkers;
- a component (iii) in form of one or more plasticizers;
- a component (iv) in form of one or more coupling agents, such as organofunctional silanes;
- optionally a component in form of one or more compounds selected from the group of ammonia, amines or any salts thereof;
- optionally a component in form of urea;
- optionally a component in form of a more reactive or non-reactive silicones;
- optionally a hydrocarbon oil;
- optionally one or more surface active agents;
- water.
- In one embodiment, the binder composition, preferably the aqueous binder composition, used according to the present invention consists essentially of
- a component (i) in form of one or more oxidized lignins;
- a component (iia) in form of one or more modifiers selected from epoxidised oils based on fatty acid triglycerides;
- a component (iv) in form of one or more coupling agents, such as organofunctional silanes;
- optionally a component in form of one or more compounds selected from the group of ammonia, amines or any salts thereof;
- optionally a component in form of urea;
- optionally a component in form of a more reactive or non-reactive silicones;
- optionally a hydrocarbon oil;
- optionally one or more surface active agents;
- water.
- The mineral fibre product of the present invention can be prepared by a common method for producing a mineral fibre product by binding mineral fibres with the binder composition. Accordingly, the mineral fibre product of the present invention is preferably prepared by a method which comprises the steps of contacting mineral fibres with an uncured and preferably aqueous binder composition comprising one or more oxidized lignins.
- In particular, the present invention also relates to a method for the manufacture of a mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001, the method comprising the steps of
- a) providing a non-cured aqueous binder composition comprising one or more oxidized lignins and water,
- b) contacting mineral fibres with the non-cured aqueous binder composition, and
- c) curing the binder composition in contact with the mineral fibers,
- In a preferred embodiment of the method of the invention, the proportion of non-purified water added is in the range of 30 to 100 wt.-%, more preferably 50 to 100 wt.-%, based on the total weight of water contained in the non-cured binder composition.
- In a further preferred embodiment of the method of the invention, the water content in the non-cured aqueous binder composition is in the range of 40 to 90 wt.-%, preferably 60 to 85 wt.-%, based on the total weight of the non-cured aqueous binder composition
- The mineral fibre product obtained in the method according to the invention can have all features which are described herein for the inventive mineral fibre product so that reference is made thereto.
- In a preferred embodiment, the non-cured aqueous binder composition comprises
- a component (i) in form of one or more oxidized lignins;
- a component (ii) in form of one or more cross-linkers;
- optionally a component (iii) in form of one or more plasticizers.
- As mentioned above, in a preferred embodiment the non-cured binder composition for use is prepared by diluting a concentrated form of the binder composition by addition of non-purified water.
- The uncured binder composition in mineral fibre product precursor such as a web where the mineral fibres are in contact with the binder composition is cured by a chemical and/or physical reaction of the binder components.
- In one embodiment, the curing takes place in a curing device.
- In one embodiment, the curing is carried out at temperatures from 100 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.
- In one embodiment, the curing takes place in a conventional curing oven for mineral wool production operating at a temperature of from 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.
- In one embodiment, the curing takes place for a time of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.
- In a typical embodiment, curing takes place at a temperature of 150 to 250 °C for a time of 30 seconds to 20 minutes.
- The curing process may commence immediately after application of the binder to the fibres. The curing is defined as a process whereby the binder composition undergoes a physical and/or chemical reaction which in case of a chemical reaction usually increases the molecular weight of the compounds in the binder composition and thereby increases the viscosity of the binder composition, usually until the binder composition reaches a solid state.
- In one embodiment the curing process comprises drying by pressure. The pressure may be applied by blowing air or gas through/over the mixture of mineral fibres and binder.
- The present invention is directed to a mineral fibre product comprising mineral fibres in contact with a cured binder composition as described above, i.e. in contact with a cured binder resulting from the curing of the binder composition, preferably aqueous binder composition, described above.
- The mineral fibres employed may be any of man-made vitreous fibres (MMVF), glass fibres, ceramic fibres, basalt fibres, slag fibres, rock fibres, stone fibres and others. These fibres may be present as a wool product, e.g. like a stone wool product. In a preferred embodiment, the mineral fibres are stone fibres or stone wool, respectively.
- The man-made vitreous fibres (MMVF) can have any suitable oxide composition. The fibres can be glass fibres, ceramic fibres, basalt fibres, slag fibres or rock or stone fibres. The fibres are preferably of the types generally known as rock, stone or slag fibres, most preferably stone fibres.
- Stone fibres commonly comprise the following oxides, in percent by weight:
- SiOz: 30 to 51
- CaO: 8 to 30
- MgO: 2 to 25
- FeO (including Fe2O3): 2 to 15
- Na2O+K2O: not more than 10
- CaO+MgO: 10 to 30
- In preferred embodiments the MMVF have the following levels of elements, calculated as oxides in wt%:
- SiOz: at least 30, 32, 35 or 37; not more than 51, 48, 45 or 43
- Al2O3: at least 12, 16 or 17; not more than 30, 27 or 25
- CaO: at least 8 or 10; not more than 30, 25 or 20
- MgO: at least 2 or 5; not more than 25, 20 or 15
- FeO (including Fe2O3): at least 4 or 5; not more than 15, 12 or 10
- FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20
- Na2O+K2O: zero or at least 1; not more than 10
- CaO+MgO: at least 10 or 15; not more than 30 or 25
- TiO2: zero or at least 1; not more than 6, 4 or 2
- TiOz+FeO: at least 4 or 6; not more than 18 or 12
- B2O3: zero or at least 1; not more than 5 or 3
- P2O5: zero or at least 1; not more than 8 or 5
- Others: zero or at least 1; not more than 8 or 5
- The MMVF made by the method of the invention preferably have the composition in wt%:
SiO2 35 to 50 Al2O3 12 to 30 TiO2 up to 2 Fe2O3 3 to 12 CaO 5 to 30 MgO up to 15 Na2O 0 to 15 K2O 0 to 15 P2O5 up to 3 MnO up to 3 B2O3 up to 3 - Another preferred composition for the MMVF is as follows in wt%:
- SiO2 39-55% preferably 39-52%
- Al2O3 16-27% preferably 16-26%
- CaO 6-20% preferably 8-18%
- MgO 1-5% preferably 1-4.9%
- NazO 0-15% preferably 2-12%
- K2O 0-15% preferably 2-12%
- R2O (Na2O + K2O) 10-14.7% preferably 10-13.5%
- P2O5 0-3% preferably 0-2%
- Fe2O3 (iron total) 3-15% preferably 3.2-8%
- B2O3 0-2% preferably 0-1%
- TiOz 0-2% preferably 0.4-1%
- Others 0-2.0%
- Glass fibres commonly comprise the following oxides, in percent by weight:
- SiO2: 50 to 70
- Al2O3: 10 to 30
- CaO: not more than 27
- MgO: not more than 12
- Glass fibres can also contain the following oxides, in percent by weight:
- Na2O+K2O: 8 to 18, in particular Na2O+K2O greater than CaO+MgO
- B2O3: 3 to 12
- Some glass fibre compositions can contain Al2O3: less than 2%.
- In a preferred embodiment, the mineral fibres are hydrophobically treated mineral fibres, preferably hydrophobically treated stone wool. The hydrophobic treatment is a common treatment and may be effected e.g. by adding at least one hydrophobic agent such as a mineral oil, a siloxane or a silicon resinduring the mineral fibre manufacturing process, forming a hydrophobic film around the fibres. Accordingly, hydrophobically treated mineral fibres preferably have a hydrophobic film on the surface thereof.
- Suitable fibre formation methods and subsequent production steps for manufacturing the mineral fibre product are those conventional in the art. Generally, the binder is sprayed immediately after fibrillation of the mineral melt on to the airborne mineral fibres. The non-cured and preferably aqueous binder composition is normally applied in an amount of 0.1 to 18%, preferably 0.2 to 8 % by weight, of the bonded mineral fibre product on a dry basis.
- The spray-coated mineral fibre web is generally cured in a curing oven by means of a hot air stream. The hot air stream may be introduced into the mineral fibre web from below, or above or from alternating directions in distinctive zones in the length direction of the curing oven.
- Typically, the curing oven is operated at a temperature of from about 150°C to about 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C. Generally, the curing oven residence time is from 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes, depending on, for instance, the product density.
- In a typical embodiment, the mineral fibre product according to the present invention is cured at a temperature of 150°C to 250°C for a time of 30 seconds to 20 minutes.
- If desired, the mineral fibre web may be subjected to a shaping process before curing. The bonded mineral fibre product emerging from the curing oven may be cut to a desired format e.g., in the form of a batt.
- In a preferred embodiment, the mineral fibre product according to the present invention is a thermal and/or acoustic insulation product, preferably a thermal insulation product.
- The mineral fibre products can have the form of a preformed pipe section, a wired mat or a slab.
- The preformed pipe section may be a in the form of a hollow cylinder or a part thereof. The dimensions of the preformed pipe section shall fit to the pipe to be insulated. Wired mats are lightly bonded mineral fibre mats stitched on galvanized wired mesh with galvanized wire.
- In a preferred embodiment, the mineral fibre product according to the present invention is a thermal and/or acoustic insulation for a pipe, a storage tank, a boiler, a vessel or a column, preferably a pipe.
- In a preferred embodiment, the mineral fibre product according to the present invention has a thickness in the range of 20 mm to 500 mm or 25 mm to 300 mm, preferably 30 mm to 300 mm, such as 50 mm to 150 mm, wherein in general the mineral fibre product is in form of a sheet.
- The mineral fibre products according to the present invention generally have a density within the range of from 6 to 250 kg/m3, preferably 20 to 200 kg/m3. The mineral fibre products generally have a loss on ignition (LOI) within the range of 0.3 to 18.0 %, preferably 0.5 to 8.0 %.
- A use according to the present invention of a mineral fibre product is directed to a use as a thermal and/or acoustic insulation, in particular as non-corrosive thermal and/or acoustic insulation.
- The term "non-corrosive" here means that the thermal and/or acoustical insulation material does not contribute to increased corrosion. "Non-corrosive" does not imply that corrosion cannot appear, but then it is caused by other factors than the thermal and/or acoustical insulation material itself.
- Accordingly, the invention also relates to a use of a mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation. It is generally preferred that the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- In a preferred embodiment of the use according to the invention, the mineral fibre product is used as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation, for an object selected from a pipe, a storage tank, a boiler, a vessel or a column, preferably a pipe. A pipe or pipework, respectively, also includes exhaust ducts.
- In a preferred embodiment of the use according to the invention, the mineral fibre product is used as a thermal and/or acoustic insulation for an object made of metal, wherein the object is generally a hollow object, for which examples are given above. The metal is preferably selected from copper or steel, wherein steel is preferred. The steel is preferably carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low alloy steel. In a particular preferred embodiment, the object is a steel pipe.
- In a preferred embodiment of the use according to the invention, the use is preferably at temperatures in the range of -20 °C to 320 °C, more preferably 0 °C to 200 °C, such as 50 °C to 175 °C. The temperature refers to the temperature of the object insulated by the mineral fibre product, i.e. the operating temperature. The operation may be continuous or cyclic with respect to the temperature. In case of cyclic operation, the above temperature range generally refers to the maximum temperature of the operation.
- The object covered by the mineral fibre product as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation, generally includes a medium which may be selected from a gas, steam or a fluid. The mineral fibre product for the use according to the invention can have all features which have been described above for the inventive mineral fibre product so that reference is made thereto.
- The invention also relates to a hollow object covered with a mineral fibre product as a thermal and/or acoustic insulation, wherein the mineral fibre product comprises mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins.
- It is preferred that the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- In a preferred embodiment, the hollow object is selected from a pipe, a storage tank, a boiler, a vessel or a column, preferably a pipe. A pipe or pipework, respectively, also includes exhaust ducts.
- In a preferred embodiment, the hollow object is made of metal. The metal is preferably selected from copper or steel, wherein steel is preferred. The steel is preferably carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low alloy steel. In a particular preferred embodiment, the object is a steel pipe.
- The mineral fibre product covering the hollow object according to the invention can have all features which have been described above for the inventive mineral fibre product so that reference is made thereto.
- Oxidised lignins which can be used as component in the binder composition, preferably the aqueous binder composition, for mineral fibres according to the present invention and method for preparing such oxidised lignins
- In the following, we describe oxidised lignins which can be used as component of the binder composition and their preparation.
- Oxidised lignins, which can be used as component for the binders used in the present invention can be prepared by a method comprising bringing into contact
- a component (a) comprising one or more lignins
- a component (b) comprising ammonia, one or more amine components, and/or any salt thereof.
- a component (c) comprising one or more oxidation agents.
- Component (a) comprises one or more lignins.
- In one embodiment of the method according to the present invention, component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof.
- In one embodiment, component (a) comprises one or more kraft lignins.
- In one embodiment according to the present invention, component (b) comprises ammonia, one or more amino components, and/or any salts thereof. Without wanting to be bound by any particular theory, the present inventors believe that replacement of the alkali hydroxides used in previously known oxidation processes of lignin by ammonia, one or more amino components, and/or any salts thereof, plays an important role in the improved properties of the oxidised lignins prepared according to the method of the present invention.
- The present inventors have surprisingly found that the lignins oxidised by an oxidation agent in the presence of ammonia or amines contain significant amounts of nitrogen as a part of the structure of the oxidised lignins. Without wanting to be bound to any particular theory, the present inventors believe that the improved fire resistance properties of the oxidised lignins when used in products where they are comprised in a binder composition, said oxidised lignins prepared by the method according to the present invention, are at least partly due to the nitrogen content of the structure of the oxidised lignins.
- In one embodiment, component (b) comprises ammonia and/or any salt thereof.
- Without wanting to be bound by any particular theory, the present inventors believe that the improved stability properties of the derivatized lignins prepared according to the present invention are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast to that, it has proven difficult to remove residual amounts of the alkali hydroxides used in the previously known oxidation process.
- Nevertheless, it can be advantageous in the method according to the present invention that component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
- In the embodiments, in which component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof, the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
- In the method according to the present invention, component (c) comprises one or more oxidation agents.
- In one embodiment, component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
- In the initial steps of the oxidation, active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained. The average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, the inventors have typically seen moderate increase of average molecular weight of around 30%.
- In one embodiment, component (c) comprises hydrogen peroxide.
- Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to radical formation:
- The present inventors have found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidised lignins prepared in the process according to the present invention plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method according to the present invention.
- Another advantage of the oxidation process is that the oxidised lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibers.
- In one embodiment, the method according to the present invention comprises further components, in particular a component (d) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
- Such oxidation catalysts can increase the rate of the reaction, thereby improving the properties of the oxidised lignins prepared by the method according to the present invention.
- The person skilled in the art will use the components (a), (b) and (c) in relative amounts that the desired degree of oxidation of the lignins is achieved.
- In one embodiment,
- a component (a) comprises one or more lignins
- a component (b) comprises ammonia
- a component (c) comprises one or more oxidation agents in form of hydrogen peroxide,
- There is more than one possibility to bring the components (a), (b) and (c) in contact to achieve the desired oxidation reaction.
- In one embodiment, the method comprises the steps of:
- a step of providing component (a) in form of an aqueous solution and/or dispersion of one more lignins, the lignin content of the aqueous solution being 1 to 50 weight-%, such as 5 to 25 weight-%, such as 15 to 22 weight-%, such as 18 to 20 weight-%, based on the total weight of the aqueous solution;
- a pH adjusting step by adding component (b) comprising an aqueous solution of ammonia, one or more amine components, and/or any salt thereof;
- an oxidation step by adding component (c) comprising an oxidation agent.
- In one embodiment, the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH ≥ 9, such as ≥ 10, such as ≥ 10.5.
- In one embodiment, the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 10.5 to 12.
- In one embodiment, the pH adjusting step is carried out so that the temperature is allowed to raise to ≥ 25 °C and then controlled in the range of 25 - 50 °C, such as 30 - 45 °C, such as 35 - 40 °C.
- In one embodiment, during the oxidation step, the temperature is allowed to raise ≥ 35 °C and is then controlled in the range of 35 - 150 °C, such as 40 - 90 °C, such as 45 - 80 °C.
- In one embodiment, the oxidation step is carried out for a time of 1 second to 48 hours, such as 10 seconds to 36 hours, such as 1 minute to 24 hours such as 2 - 5 hours.
- Oxidised lignins, which can be used as component for the binders used in the present invention can be prepared by a method comprising bringing into contact
- a component (a) comprising one or more lignins
- a component (b) comprising ammonia and/or one or more amine components, and/or any salt thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide
- a component (c) comprising one or more oxidation agents
- a component (d) in form of one or more plasticizers.
- Component (a) comprises one or more lignins.
- In one embodiment of the method according to the present invention, component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof.
- In one embodiment, component (a) comprises one or more kraft lignins.
- In one embodiment according to the present invention, component (b) comprises ammonia, one or more amino components, and/or any salts thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
- "Ammonia-oxidized lignins" is to be understood as a lignin that has been oxidized by an oxidation agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.
- In one embodiment, component (b) comprises ammonia and/or any salt thereof.
- Without wanting to be bound by any particular theory, the present inventors believe that the improved stability properties of the derivatized lignins prepared according to the present invention with component (b) being ammonia and/or any salt thereof are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused.
- Nevertheless, it can be advantageous in this embodiment of the method according to the present invention that component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
- In the embodiments, in which component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof, the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
- In the method according to the present invention, component (c) comprises one or more oxidation agents.
- In one embodiment, component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
- In the initial steps of the oxidation, active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism, multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained. The average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, the inventors have typically seen moderate increase of average molecular weight of around 30%.
- In one embodiment, component (c) comprises hydrogen peroxide.
- Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to radical formation:
- The present inventors have found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidized lignins prepared in the process according to the present invention plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method according to the present invention.
- Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibres.
- Component (d) comprises one or more plasticizers.
- In one embodiment according to the present invention, component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea., or any mixtures thereof.
- The present inventors have found that the inclusion of component (d) in form of one or more plasticizers provides a decrease of the viscosity of the reaction mixture which allows a very efficient method to produce oxidised lignins.
- In one embodiment according to the present invention, component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
- In one embodiment according to the present invention, component (d) comprises one or more plasticizers selected from the group of polyethylene glycols, polyvinyl alcohol, urea or any mixtures thereof.
- In one embodiment, the method according to the present invention comprises further components, in particular a component (v) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
- Such oxidation catalysts can increase the rate of the reaction, thereby improving the properties of the oxidized lignins prepared by the method.
- The person skilled in the art will use the components (a), (b), (c), and (d) in relative amounts that the desired degree of oxidation of the lignins is achieved.
- In one embodiment, the method according to the present invention is carried out such that the method comprises
- a component (a) comprises one or more lignins
- a component (b) comprises ammonia
- a component (c) comprises one more oxidation agents in form of hydrogen peroxide,
- a component (d) comprises one or more plasticizers selected from the group of polyethylene glycol,
- For the purpose of the present invention, the "dry weight of lignin" is preferably defined as the weight of the lignin in the supplied form.
- There is more than one possibility to bring the components (a), (b), (c), and (d) in contact to achieve the desired oxidation reaction.
- In one embodiment, the method comprises the steps of:
- a step of providing component (a) in form of an aqueous solution and/or dispersion of one more lignins, the lignin content of the aqueous solution being 5 to 90 weight-%, such as 10 to 85 weight-%, such as 15 to 70 weight-%, based on the total weight of the aqueous solution;
- a pH adjusting step by adding component (b);
- a step of adding component (d);
- an oxidation step by adding component (c) comprising an oxidation agent.
- In one embodiment, the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH ≥ 9, such as ≥ 10, such as ≥ 10.5.
- In one embodiment, the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 9.5 to 12.
- In one embodiment, the pH adjusting step is carried out so that the temperature is allowed to raise to ≥ 25 °C and then controlled in the range of 25 - 50 °C, such as 30 - 45 °C, such as 35 - 40 °C.
- In one embodiment, during the oxidation step, the temperature is allowed to raise to ≥ 35 °C and is then controlled in the range of 35 - 150 °C, such as 40 - 90 °C, such as 45 - 80 °C.
- In one embodiment, the oxidation step is carried out for a time of 1 seconds to 24 hours, such as 1 minutes to 12 hours, such as 10 minutes to 8 hours, such as 5 minutes to 1 hour.
- The present inventors have found that the process according to the present invention allows to produce a high dry matter content of the reaction mixture and therefore a high throughput is possible in the process according to the present invention which allows the reaction product in form of the oxidised lignins to be used as a component in industrial mass production products such as mineral fibre products.
- In one embodiment, the method according to the present invention is carried out such that the dry matter content of the reaction mixture is 20 to 80 wt.%, such as 40 to 70 wt.%.
- In one embodiment, the method according to the present invention is carried out such that the viscosity of the oxidised lignin has a value of 100 cP to 100.000 cP, such as a value of 500 cP to 50.000 cP, such as a value of 1.000 cP to 25.000 cP.
- For the purpose of the present invention, viscosity is dynamic viscosity and is defined as the resistance of the liquid/paste to a change in shape, or movement of neighbouring portions relative to one another. The viscosity is measured in centipoise (cP), which is the equivalent of 1 mPa s (milipascal second). Viscosity is measured at 20°C using a viscometer. For the purpose of the present invention, the dynamic viscosity can be measured at 20°C by a Cone Plate Wells Brookfield Viscometer.
- In one embodiment, the method according to the present invention is carried out such that the method comprises a rotator-stator device.
- In one embodiment, the method according to the present invention is carried out such that the method is performed as a continuous or semi-continuous process.
- The present invention is also directed to an apparatus for performing the method described above.
- In one embodiment, the apparatus for performing the method comprises:
- a rotor-stator device,
- a premixing device for component (a), (b), (d)
- one or more inlets for water, components (a), (b), (c) and (d),
- one or more outlets for an oxidised lignin.
- In one embodiment, the apparatus is constructed in such a way that the inlets for the premix of the components (a), (b) and (d) are to the rotor-stator device and the apparatus furthermore comprises a chamber,
- said chamber having an inlet for component (c) and
- said chamber having an outlet for an oxidised lignin.
- A rotator-stator device is a device for processing materials comprising a stator configured as an inner cone provided with gear rings. The stator cooperates with a rotor having arms projecting from a hub. Each of these arms bears teeth meshing with the teeth of the gear rings of the stator. With each turn of the rotor, the material to be processed is transported farther outward by one stage, while being subjected to an intensive shear effect, mixing and redistribution. The rotor arm and the subjacent container chamber of the upright device allow for a permanent rearrangement of the material from the inside to the outside and provide for a multiple processing of dry and/or highly viscous matter so that the device is of excellent utility for the intensive mixing, kneading, fibrillating, disintegrating and similar processes important in industrial production. The upright arrangement of the housing facilitates the material's falling back from the periphery toward the center of the device.
- In one embodiment, the rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow. At the rotor, a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
- For more details of the rotator-stator device to be used in one embodiment of the method, reference is made to
US 2003/0042344 A1 , which is incorporated by reference. - In one embodiment, the method is carried out such that the method uses one rotator-stator device. In this embodiment, the mixing of the components and the reaction of the components is carried out in the same rotator-stator device.
- In one embodiment, the method is carried out such that the method uses two or more rotator-stator devices, wherein at least one rotator-stator device is used for the mixing of the components and at least one rotator-stator device is used for reacting the components.
- This process can be divided into two steps:
- 1. Preparation of the Lignin mass (a)+(b)+(d)
- 2. Oxidization of the lignin mass
- Typically, two different types of rotor-/stator machines are used:
- 1. Open rotor-/stator machine suitable for blending in the lignin powder into water on a very high concentration (30 to 50 wt-%). Less intensive mixing but special auxiliaries (inlet funnel, screw etc.) to handle highly viscous materials. Lower circumferential speed (up to 15 m/s). The machine can be used as batch system or continuous.
- 2. Inline rotor-/stator machine which has much higher shear forces - circumferential speeds of up to 55 m/s) - and creates beneficial conditions for a very quick chemical reaction. The machine is to be used continuously.
- In the open rotor-/stator system the highly concentrated (45 to 50 wt-%) mass of Lignin/water is prepared. The lignin powder is added slowly to the warm water (30 to 60 deg.C) in which the correct amount of watery ammonia and/or alkali base have been added. This can be done in batch mode, or the materials are added intermittently/continuously creating a continuous flow of mass to the next step.
- The created mass should be kept at a temperature of about 60 deg. to keep the viscosity as low as possible and hence the material pumpable. The hot mass of lignin/water at a pH of 9 to 12 is then transferred using a suitable pump, e.g. progressive cavity pump or another volumetric pump, to the oxidation step.
- In on embodiment the oxidation is done in a closed rotor-/stator system in a continuous inline reaction. A watery solution of ammonia and/or alkali base is dosed with a dosing pump into the rotor-/stator chamber at the point of highest turbulence/shear. This ensures a rapid oxidation reaction. The oxidized material (AOL) leaves the inline-reactor and is collected in suitable tanks.
- The present inventors have surprisingly found, that the oxidized lignins prepared have very desirable reactivity properties and at the same time display improved fire resistance properties when used in products where they are comprised in a binder composition, and improved long term stability over previously known oxidized lignins.
- The oxidised lignin also displays improved hydrophilicity.
- An important parameter for the reactivity of the oxidized lignins prepared is the carboxylic acid group content of the oxidized lignins.
- In one embodiment, the oxidized lignin prepared has a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 2.0 mmol/g, such as 0.40 to 1.5 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (a).
-
- In one embodiment, the oxidized lignin prepared has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (a), such as more than 2 groups, such as more than 2.5 groups.
- Oxidised lignins, which can be used as a component for the binder used in the present invention can be prepared by a method comprising bringing into contact
- a component (a) comprising one or more lignins,
- a component (b) comprising ammonia and/or one or more amine components, and/or any salt thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide,
- a component (c) comprising one or more oxidation agents,
- optionally a component (d) in form of one or more plasticizers,
- Components (a), (b), (c) and (d) are as defined above under Method II to prepare oxidised lignins.
- In one embodiment of the invention, the process comprises a premixing step in which components are brought into contact with each other.
- In the premixing step the following components can be brought into contact with each other:
- component (a) and component (b), or
- component (a) and component (b) and component (c), or
- component (a) and component (b) and component (d), or
- component (a) and component (b) and component (c) and component (d).
- In an embodiment of the invention, it is possible that the premixing step is carried out as a separate step and the mixing/oxidation step is carried out subsequently to the premixing step. In such an embodiment of the invention it is particularly advantageous to bring component (a) and component (b) and optionally component (d) into contact with each other in a premixing step. In a subsequent mixing/oxidation step, component (c) is then added to the premixture produced in the premixing step.
- In another example of the invention, it is possible that the premixing step corresponds to the mixing/oxidation step. In this embodiment of the invention, the components, for example component (a), component (b) and component (c) are mixed and an oxidation process is started at the same time. It is possible that the subsequent dwell time is performed in the same device as that used to perform the mixing/oxidation step. Such an implementation of the invention is particularly advantageous if component (c) is air.
- The present inventors have found out that by allowing a mixing/oxidation step followed by an oxidation step, in which the reaction mixture is preferably not continued to be mixed, the oxidation rate can be controlled in a very efficient manner. At the same time, the costs for performing the method are reduced because the oxidation step subsequent to the mixing/oxidation step requires less complex equipment.
- Another advantage is that oxidized lignin, which is produced is particularly stable. Another surprising advantage is that the oxidized lignin produced is very well adjustable in terms of viscosity. Another surprising advantage is that the concentration of the oxidized lignin can be very high.
- In one embodiment, the dwell time is so chosen that the oxidation reaction is brought to the desired degree of completion, preferably to full completion.
- In one embodiment, the system for performing the method comprises:
- at least one rotor-stator device,
- one or more inlets for water and components (a) and (b),
- one or more outlets of the rotor-stator device,
- at least one reaction device, in particular at least one reaction tube, which is arranged downstream in the process flow direction to at least one or more of the outlets.
- In one embodiment, the system comprises one or more inlets for component (c) and/or component (d).
- In one embodiment, the system comprises a premixing device.
- The premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
- In one embodiment of the invention, the premixing device comprises inlets for water and component (a) and component (b).
- It is possible that, in a premixing step, component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
- In one embodiment, the system is constructed in such a way that
- the inlets for components (a), (b) and (d) are inlets of a premixing device, in particular of an open rotor-stator device,
- whereby the system furthermore comprises an additional rotor-stator device, said additional rotor-stator device having an inlet for component (c) and said additional rotor-stator device having an outlet for an oxidized lignin.
- It is possible that the premixing step and the mixing/oxidizing step are carried out simultaneously. In this case, the premixing device and the mixing/oxidizing device are a single device, i. e. a rotor-stator device.
- In one embodiment, one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow. At the rotor, a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
- In one embodiment, the system for performing the method comprises:
- one or more inlets for water, components (a) and (b),
- at least one mixing and oxidizing apparatus with one or more outlets, and
- at least one mixer/heat-exchanger, which is arranged downstream in the process flow direction to the at least one or more of the outlets, whereby the mixer/heat-exchanger comprises a temperature control device.
- In one embodiment, the system comprises additional one or more inlets for component (c) and/or component (d).
- In one embodiment, the system comprises a premixing device.
- The premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
- In one embodiment, the premixing device comprises inlets for water and component (a) and component (b).
- It is possible that, in a premixing step, component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
- In one embodiment, the system is constructed in such a way that the inlets for components (a), (b) and (d) are inlets of an open rotor-stator device, whereby the system furthermore comprises a mixer/heat-exchanger, having an inlet for component (c) and an outlet for an oxidized lignin.
- It is possible that the premixing step and the mixing/oxidizing step are carried out simultaneously. In this case, the premixing device and the mixing/oxidizing device are a single device.
- In one embodiment, one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow. At the rotor, a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
- Of course other devices can also be used as premixing devices. Furthermore, it is possible that the premixing step is carried out in the mixing and oxidizing apparatus.
- In one embodiment, the mixing and oxidizing apparatus is a static mixer. A static mixer is a device for the continuous mixing of fluid materials, without moving components. One design of static mixer is the plate-type mixer and another common device type consists of mixer elements contained in a cylindrical (tube) or squared housing.
- In one embodiment, the mixer/heat-exchanger is constructed as multitube heat exchanger with mixing elements. The mixing element are preferably fixed installations through which the mixture has to flow, whereby mixing is carried out as a result of the flowing through. The mixer/heat-exchanger can be constructed as a plug flow reactor.
- The amounts of ingredients used according to the example IA are provided in table IA 1.1 and IA 1.2.
- Although kraft lignin is soluble in water at relatively high pH, it is known that at certain weight percentage the viscosity of the solution will strongly increase. It is typically believed that the reason for the viscosity increase lies in a combination of strong hydrogen bonding and interactions of n-electrons of numerous aromatic rings present in lignin. For kraft lignin an abrupt increase in viscosity around 21-22 wt.-% in water was observed and 19 wt.-% of kraft lignin were used in the example presented.
- Ammonia aqueous solution was used as base in the pH adjusting step. The amount was fixed at 4 wt.-% based on the total reaction weight. The pH after the pH adjusting step and at the beginning of oxidation was 10.7.
- Table IA2 shows the results of CHNS elemental analysis before and after oxidation of kraft lignin. Before the analysis, the samples were heat treated at 160 °C to remove adsorbed ammonia. The analysis showed that a certain amount of nitrogen became a part of the structure of the oxidised lignin during the oxidation process.
- During testing in batch experiments, it was determined that it is beneficial for the oxidation to add the entire amount of hydrogen peroxide during small time interval contrary to adding the peroxide in small portions over prolonged time period. In the present example 2.0 wt.-% of H2O2 based on the total reaction weight was used.
- The oxidation is an exothermic reaction and increase in temperature is noted upon addition of peroxide. In this example, temperature was kept at 60 °C during three hours of reaction.
- After the oxidation, the amount of lignin functional groups per gram of sample increased as determined by 31P NMR and aqueous titration. Sample preparation for 31P NMR was performed by using 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) as phosphitylation reagent and cholesterol as internal standard. NMR spectra of kraft lignin before and after oxidation were made and the results are summarized in table IA3.
-
- Where V2s and V1s are endpoint volumes of a sample while V2b and V1b are the volume for the blank. Cacid is 0.1M HCl in this case and ms is the weight of the sample. The values obtained from aqueous titration before and after oxidation are shown in table IA4.
- The average COOH functionality can also be quantified by a saponification value which represents the number of mg of KOH required to saponify 1 g lignin. Such a method can be found in AOCS Official Method Cd 3-25.
- Average molecular weight was also determined before and after oxidation with a PSS PolarSil column (9:1 (v/v) dimethyl sulphoxide/water eluent with 0.05 M LiBr) and UV detector at 280nm. Combination of COOH concentration and average molecular weight also allowed calculating average carboxylic acid group content per lignin macromolecule and these results are shown in table IA5.
- Lignin oxidation with hydrogen peroxide is an exothermic process and even in lab-scale significant temperature increases were seen upon addition of peroxide. This is a natural concern when scaling up chemical processes since the amount of heat produced is related to dimensions in the 3rd power (volume) whereas cooling normally only increase with dimension squared (area). In addition, due to the high viscosity of the adhesive intermediates process equipment has to be carefully selected or designed. Thus, the scale up was carefully engineered and performed in several steps.
- The first scale up step was done from 1 L (lab scale) to 9 L using a professional mixer in stainless steel with very efficient mechanical mixing The scale-up resulted only in a slightly higher end temperature than obtained in lab scale, which was attributed to efficient air cooling of the reactor and slow addition of hydrogen peroxide
- The next scale up step was done in a closed 200 L reactor with efficient water jacket and an efficient propeller stirrer. The scale was this time 180 L and hydrogen peroxide was added in two steps with appr. 30 minute separation. This up-scaling went relatively well, though quite some foaming was an issue partly due to the high degree reactor filling. To control the foaming a small amount of food grade defoamer was sprayed on to the foam. Most importantly the temperature controllable and end temperatures below 70 °C were obtained using external water-cooling.
- The pilot scale reactions were performed in an 800 L reactor with a water cooling jacket and a twin blade propeller stirring. 158 kg of lignin (UPM LignoBoost TM BioPiva 100) with a dry-matter content of 67 wt.-% was de-lumped and suspended in 224 kg of water and stirred to form a homogenous suspension. With continued stirring 103 kg of 25% ammonia in water was pumped into the reactor and stirred another 2 hours to from a dark viscous solution of lignin.
- To the stirred
lignin solution 140 kg of 7.5wt.-% at 20-25 °C hydrogen peroxide was added over 15 minutes. Temperature and foam level was carefully monitored during and after the addition of hydrogen peroxide and cooling water was added to the cooling jacket in order to maintain an acceptable foam level and a temperature rise less than 4 °C per minute as well as a final temperature below 70 °C. After the temperature increase had stopped, cooling was turned off and the product mixture was stirred for another 2 hours before transferring to transport container. - Based on the scale up runs it could be concluded that even though the reactions are exothermic a large part of the reaction heat is actually balanced out by the heat capacity of the water going from room temperature to about 60 °C, and only the last part has to be removed by cooling. It should be noted that due to this and due to the short reaction time this process would be ideal for a scale up and process intensification using continuous reactors such as in- line mixers, tubular reactors or CSTR type reactors. This would ensure good temperature control and a more well-defined reaction process.
- Tests of the scale up batches indicated the produced oxidised lignin had properties in accordance to the batches produced in the lab.
Table IA 1.1 The amounts of materials used in their supplied form: material wt.-% UPM BioPiva 100, kraft lignin 28 H2O2, 30 wt.-% solution in water 6.6 NH3, 25wt.-%, aqueous solution 16 water 49.4 Table IA 1.2 The amounts of active material used: material wt.-% kraft lignin 19 H2O2 2 NH3 4 water 75 Table IA 2 Elemental analysis of kraft lignin before and after oxidation: sample N (wt.-%) C (wt.-%) H (wt.-%) S (wt.-%) kraft lignin 0.1 64.9 5.8 1.7 ammonia oxidised kraft lignin 1.6 65.5 5.7 1.6 Table IA 3 Kraft lignin functional group distribution before and after oxidation obtained by 31P-NMR: sample Concentration (mmol/g) Aliphatic OH Phenolic OH Acid OH kraft lignin 1.60 3.20 0.46 ammonia oxidised kraft lignin 2.11 3.60 0.80 Table IA 4 COOH group content in mmol/g as determined by aqueous titration: sample COOH groups (mmol/g) kraft lignin 0.5 ammonia oxidised kraft lignin 0.9 Table IA 5Table IA 5. Number (Mn) and weight (Mw) average molar masses as determined by size exclusion chromatography expressed in g/mol together with average carboxylic acid group content per lignin macromolecule before and after oxidationsample Mn, g/mol Mw, g/mol average COOH functionality kraft lignin 1968 21105 0.9 ammonia oxidised kraft lignin 2503 34503 2.0 - In the following examples, several oxidised lignins were prepared.
- The following properties were determined for the oxidised lignins:
- The content of each of the components in a given oxidised lignin solution is based on the anhydrous mass of the components or as stated below.
- Kraft lignin was supplier by UPM as BioPiva100™ as dry powder. NH4OH 25% was supplied by Sigma-Aldrich and used in supplied form. H2O2, 30% (Cas no 7722-84-1) was supplied by Sigma-Aldrich and used in supplied form or by dilution with water. PEG 200 was supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such. PVA (Mw 89.000-98.000, Mw 85.000-124.000, Mw 130.000, Mw 146.000-186.000) (Cas no 9002-89-5) were supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such. Urea (Cas no 57-13-6) was supplied by Sigma-Aldrich and used in supplied form or diluted with water. Glycerol (Cas no 56-81-5) was supplied by Sigma-Aldrich and was assumed anhydrous for simplicity and used as such.
- The content of the oxidised lignin after heating to 200 °C for 1h is termed "Dry solid matter" and stated as a percentage of remaining weight after the heating.
- Disc-shaped stone wool samples (diameter: 5 cm;
height 1 cm) were cut out of stone wool and heat-treated at 580 °C for at least 30 minutes to remove all organics. The solids of the binder mixture were measured by distributing a sample of the binder mixture (approx. 2 g) onto a heat treated stone wool disc in a tin foil container. The weight of the tin foil container containing the stone wool disc was weighed before and directly after addition of the binder mixture. Two such binder mixture loaded stone wool discs in tin foil containers were produced and they were then heated at 200 °C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the dry solids matter was calculated as an average of the two results. -
- Where V2s and V1s are endpoint volumes of a sample while V2b and V1b are the volume for a blank sample. Cacid is 0.1M HCl in this case and ms,g is the weight of the sample.
- Method of producing an oxidised lignin:
- 1) Water and lignin was mixed in a 3-necked glass bottomed flask at water bath at room temperature (20-25°C) during agitation connected with a condenser and a temperature logging device. Stirred for 1h.
- 2) Ammonia was added during agitation in 1 portion.
- 3) Temperature increased to 35°C by heating, if the slightly exothermic reaction with ammonia does not increase the temperature.
- 4) pH was measured.
- 5) Plasticizer PEG200 was added and stirred 10 min.
- 6) After the lignin was completely dissolved after approximately 1 hour, 30% H2O2 was added slowly in one portion.
- 7) The exothermic reaction by addition of H2O2 increased the temperature in the glass bottomed flask - if the reaction temperature was lower than 60C, the temperature was increased to 60°C and the sample was left at 60°C for 1 hour.
- 8) The round bottomed flask was then removed from the water bath and cooled to room temperature.
- 9) Samples were taken out for determination of dry solid matter, COOH, viscosity, density and pH.
- In the following, the entry numbers of the oxidised lignin example correspond to the entry numbers used in Table II.
- 71,0 g lignin UPM Biopiva 100 was dissolved in 149,0 g water at 20°C and added 13,3 g 25% NH4OH and stirred for 1h by magnetic stirrer, where after 16,8g H2O2 30% was added slowly during agitation. The temperature was increased to 60°C in the water bath. After 1h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
- 71,0 g lignin UPM Biopiva 100 was dissolved in 88,8 g water at 20°C and added 13,3 g 25% NH4OH and stirred for 1h by magnetic stirrer. PEG 200, 22,8g was added and stirred for 10 min, where after 16,7 g H2O2 30% was added slowly during agitation. The temperature was increased to 60°C in the water bath. After 1h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
- 71,0 g lignin UPM Biopiva 100 was dissolved in 57,1 g water at 20°C and added 13,3 g 25% NH4OH and stirred for 1h by mechanical stirrer, where after 16,6 g H2O2 30% was added slowly during agitation. The temperature was increased to 60°C in the water bath. After 1h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
- 71,0 g lignin UPM Biopiva 100 was dissolved in 57,1 water at 20°C and added 13,3 g 25% NH4OH and stirred for 1h by mechanical stirrer. PEG 200, 19,0 g was added and stirred for 10 min, where after 16,6g H2O2 30% was added slowly during agitation. The temperature was increased to 60°C in the water bath. After 1h of oxidation, the water bath was cooled and hence the reaction was stopped. The resulting material was analysed for COOH, dry solid matter, pH, viscosity and density.
TABLE IIA Example Ex. IIA Ex. IIB Ex. IIC Ex. IID Ex. IIE Ex. IIF Ex. IIG Ex. IIH Ex. III Ex. IIJ Ex. IIK Ex. IIL Ex. IIM Ex. IIN Ex. IIO Ex. IIP Ex. IIQ Ex. IIP Ex. IIS Materials, weight in grams: Lignin 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 71,0 93,5 112,3 149,5 Water 149,0 88,8 57,1 17,7 88,8 57,1 17,7 88,8 57,1 17,7 88,8 57,1 17,7 88,8 57,1 17,7 117 90,3 37,3 NH4OH (25 wt% solution in water) 13,3 13,3 13,3 13,4 13,3 13,3 13,4 13,3 13,3 13,4 13,3 13,3 13,4 13,3 13,3 13,4 17,5 21 28,3 H2O2 (30 wt% solution in water) 16,8 16,7 16,6 17,2 16,7 16,6 17,2 16,7 16,6 17,2 16,7 16,6 17,2 16,7 16,6 17,2 22 26,3 36,3 PEG200 0,0 0,0 0,0 0,0 22,8 19,0 14,2 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 PVA 0 0 0 0 0 0 0 5 10 15 0 0 0 0 0 0 0 0 0 Urea (25 wt% solution in water) 0 0 0 0 0 0 0 0 0 0 3,2 3,8 5,0 0 0 0 0 0 0 Glycerol 0 0 0 0 0 0 0 0 0 0 0 0 0 16,0 21,0 30,0 0 0 Sorbitol 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 16,0 21,0 Dry solid matter in %, 200°C, 1h 18,2 27,1 30,5 40,1 26,5 33 40,3 28,2 34,4 46,3 25,1 30,2 40,2 25,3 29,3 40,3 25,3 30,5 38,8 pH 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 9,5 Viscosity, 20°C cP 450,5 25000 above 100000 above 100000 15000 25000 50000 15000 25000 50000 15000 25000 50000 15000 25000 50000 15000 25000 50000 Appearance ** *** * * *** *** *** *** *** *** *** *** *** *** *** *** *** *** *** COOH, mmol/g 1,1 0,9 0,9 0,8 0,8 1,9 - - - - - - - - - - - - - Initial lignin cone. Weight fraction of aq. sol. 0,32 0,44 0,55 0,80 0,44 0,55 0,80 0,44 0,55 0,80 0,44 0,55 0,80 0,44 0,55 0,80 0,44 0,55 0,80 [*] inhomogenous black thick solution; [**] black solution; [***] homogenous black thick solution. - 8,5 l hot water (50 °C) and 1,9 l NH4OH (24,7%) was mixed, where after 9,0 kg lignin (UPM biopiva 100) was added slowly over 10 minutes at high agitation (660 rpm, 44 Hz).
- The temperature increased by high shear forces. After 30 minutes, 4 l of hot water was added, and the material was stirred for another 15 minutes before adding the remaining portion of hot water (5 l). Samples were taken out for analyses of un-dissolved lignin by use of a Hegman Scale and pH measurements.
- This premix was then transferred to a rotor-stator device and a reaction device where the oxidation was made by use of H2O2 (17,5 vol%). The reaction device used in this case has at least partially a reaction tube and a reaction vessel. Dosage of the premixture was 150 l/h and the H2O2 was dosed at 18 l/h.
- In the present case, a Cavitron CD1000 rotor-stator device was used to carry out the mixing/oxidation step. The rotor-stator device was run at 250 Hz (55 m/s circumferential speed) with a counter pressure at 2 bar. The dwell time in the reaction tube was 3,2 minutes and in the reaction vessel 2 hours.
- Temperature of the premixture was 62 °C, and the oxidation step increased the temperature to 70°C.
- The final product was analysed for the COOH group content, dry solid matter, pH, viscosity and remaining H2O2.
Table III: Example Dry solid matter, 200C, 1h, % COOH, mmol/g solids pH viscosity III 22,3 1,13 9,6 medium - 484 l hot water (70 °C) and 47,0 l NH4OH (24,7 %) was mixed, where after 224,0 kg lignin (UPM biopiva 100) was added slowly over 15 minutes at high agitation. Samples were taken out for analyses of un-dissolved lignin by use of a Hegman Scale and pH measurements.
- This premixture was then transferred to a static mixer and a mixer/heat-exchanger, where the oxidation was made by use of H2O2 (35 vol%). Dosage of the premixture was 600 l/h and the H2O2 was dosed at 17,2 l/h. The dwell time in the mixer/heat-exchanger was 20 minutes.
- The temperature of the mixture increased during the oxidation step up to 95 °C.
- The final product was analysed for the COOH group content, dry solid matter, pH, viscosity and remaining H2O2.
- A binder was made based on this AOL: 49,3 g AOL (19,0 % solids), 0,8 g primid XL552 (100 % solids) and 2,4 g PEG200 (100 % solids) were mixed with 0,8 g water to yield 19% solids; and then used for test of mechanical properties in bar tests.
- The mechanical strength of the binders was tested in a bar test. For each binder, 16 bars were manufactured from a mixture of the binder and stone wool shots from the stone wool spinning production.
- A sample of this binder solution having 15% dry solid matter (16.0 g) was mixed well with shots (80.0 g). The resulting mixture was then filled into four slots in a heat resistant silicone form for making small bars (4×5 slots per form; slot top dimension: length = 5.6 cm, width = 2.5 cm; slot bottom dimension: length = 5.3 cm, width = 2.2 cm; slot height = 1.1 cm). The mixtures placed in the slots were then pressed with a suitably sized flat metal bar to generate even bar surfaces. 16 bars from each binder were made in this fashion. The resulting bars were then cured at 200 °C. The curing time was 1 h. After cooling to room temperature, the bars were carefully taken out of the containers. Five of the bars were aged in a water bath at 80 °C for 3 h.
- After drying for 1-2 days, the aged bars as well as five unaged bars were broken in a 3 point bending test (test speed: 10.0 mm/min; rupture level: 50%; nominal strength: 30 N/mm2; support distance: 40 mm; max deflection 20 mm; nominal e-module 10000 N/mm2) on a Bent Tram machine to investigate their mechanical strengths. The bars were placed with the "top face" up (i.e. the face with the dimensions length = 5.6 cm, width = 2.5 cm) in the machine.
AOL characteristica Bar tests Sample name solids, 200C, 1h, % COOH (mmol/g solids) Viscosity initial strength (kN) Aged strength (kN) Ex IV 17,7 1,69 low 0,28 0,11 - The following examples are intended to further illustrate the invention without limiting its scope.
- In the following examples, several binders which fall under the definition of the present invention were prepared and compared to binders according to the prior art.
- The following properties were determined for the binders according to the present invention and the binders according to the prior art, respectively:
- The water leachable chloride content of the mineral fibre product is measured according to EN 13468:2001. The standard specifies the equipment and procedures for determining trace quantities of the water soluble chloride in an aqueous extract of the product. Reference is made thereto. The water leachable chloride content is given in mg chloride per kg mineral fibre product.
- The quantity of organic material (loss of ignition) is determined as the loss of weight of the specimen obtained by burning away of organic material. This is done as specified in EN 13820. The binder content is taken as the LOI. The binder includes oil and other binder additives, if present.
- The content of binder after curing is termed "binder solids".
- Disc-shaped stone wool samples (diameter: 5 cm;
height 1 cm) were cut out of stone wool and heat-treated at 580 °C for at least 30 minutes to remove all organics. The solids of the binder mixture was measured by distributing a sample of the binder mixture (approx. 2 g) onto a heat treated stone wool disc in a tin foil container. The weight of the tin foil container containing the stone wool disc was weighed before and directly after addition of the binder mixture. Two such binder mixture loaded stone wool discs in tin foil containers were produced and they were then heated at 200 °C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the binder solids was calculated as an average of the two results. - Unless stated otherwise, the following reagents were used as received:
- Lignin UPM BioPiva 100: Kraft lignin supplied by UPM as BioPiva100™ as dry powder.
- PEG 200: supplied by Sigma-Aldrich and assumed anhydrous for simplicity and used as such.
- Primid XL552: hydroxyalkylamide crosslinker supplied by EMS-CHEMIE AG
- 3267 kg of water is charged in 6000 l reactor followed by 287 kg of ammonia water (24.7%). Then 1531 kg of Lignin UPM BioPiva 100 is slowly added over a period of 30 min to 45 min. The mixture is heated to 40°C and kept at that temperature for 1 hour. After 1 hour a check is made on insolubilized lignin. This can be made by checking the solution on a glass plate or a Hegman gauge. Insolubilized lignin is seen as small particles in the brown binder. During the dissolution step will the lignin solution change color from brown to shiny black.
- After the lignin is completely dissolved, 1 liter of a foam dampening agent (Skumdaemper 11-10 from NCA-Verodan) is added. Temperature of the batch is maintained at 40°C.
- Then addition of 307,5 kg 35% hydrogen peroxide is started. The hydrogen peroxide is dosed at a rate of 200-300 liter/hour. First half of the hydrogen peroxide is added at a rate of 200 l/h where after the dosage rate is increased to 300 liter/hour.
- During the addition of hydrogen peroxide the temperature in the reaction mixture is controlled by heating or cooling in such a way that a final reaction temperature of 65°C is reached.
- After 15 min reaction at 65°C is the reaction mixture cooled to a temperature below 50°C. Hereby is a resin obtained having a COOH value of 1.2 mmol/g solids.
- From the above mentioned AOL resin a binder was formulated by addition of 270 kg polyethylene glycol 200 (PEG 200) and 433 kg of a 31% solution of Primid XL-552 in water.
- Analysis of the final binder showed the following data
- Solids content: 18.9%
- pH: 9.7
- Viscosity: 25.5 mPas.s
- Density: 1.066 kg/l
- This binder is a phenol-formaldehyde resin modified with urea, a PUF-resol.
- A phenol-formaldehyde resin is prepared by reacting 37% aq. formaldehyde (606 g) and phenol (189 g) in the presence of 46% aq. potassium hydroxide (25.5 g) at a reaction temperature of 84°C preceded by a heating rate of approximately 1°C per minute. The reaction is continued at 84 °C until the acid tolerance of the resin is 4 and most of the phenol is converted. Urea (241 g) is then added and the mixture is cooled.
- The acid tolerance (AT) expresses the number of times a given volume of a binder can be diluted with acid without the mixture becoming cloudy (the binder precipitates). Sulfuric acid is used to determine the stop criterion in a binder production and an acid tolerance lower than 4 indicates the end of the binder reaction.
- To measure the AT, a titrant is produced from diluting 2.5 ml conc. sulfuric acid (>99 %) with 1 L ion exchanged water. 5 mL of the binder to be investigated is then titrated at room temperature with this titrant while keeping the binder in motion by manually shaking it; if preferred, use a magnetic stirrer and a magnetic stick. Titration is continued until a slight cloud appears in the binder, which does not disappear when the binder is shaken.
-
- Using the urea-modified phenol-formaldehyde resin obtained, a binder is made by addition of 25% aq. ammonia (90 mL) and ammonium sulfate (13.2 g) followed by water (1.30 kg).
- To the above mix is added 18% Dextrose (127.5 g) based upon the dry matter of the above binder and the dextrose. The binder solids were then measured as described above and the mixture was diluted with the required amount of water and silane (15 % binder solids solution, 0.5% silane of binder solids) for production of an insulation product.
- Depending on the type of dilution water used reference binder A1 (rain water), A2 (process water), A5 (osmosis water) was obtained.
- Made as described in example A1, but without addition of dextrose. For binder example A3 process water is used, and for A4 osmosis water.
- A mixture of 75.1% aq. glucose syrup (19.98 kg; thus efficiently 15.0 kg glucose syrup), 50% aq. hypophosphorous acid (0.60 kg; thus efficiently 0.30 kg, 4.55 mol hypophosphorous acid) and sulfamic acid (0.45 kg, 4.63 mol) in water (30.0 kg) was stirred at room temperature until a clear solution was obtained. 28% aq. ammonia (0.80 kg; thus efficiently 0.22 kg, 13.15 mol ammonia) was then added dropwise until pH = 7.9. The binder solids was then measured (21.2%). For mechanical strength studies (15 % binder solids solution, 0.5% silane of binder solids), the binder mixture was diluted with water (0.403 kg / kg binder mixture) and 10% aq. silane (0.011 kg / kg binder mixture, Momentive VS-142). The final binder mixture for had pH = 7.9 and was used for production of an insulation product.
- 3267 kg of water is charged in 6000 l reactor followed by 287 kg of ammonia water (24.7%). Then 1531 kg of Lignin UPM BioPiva 100 is slowly added over a period of 30 min to 45 min. The mixture is heated to 40°C and kept at that temperature for 1 hour. After 1 hour a check is made on insolubilized lignin. This can be made by checking the solution on a glass plate or a Hegman gauge. Insolubilized lignin is seen as small particles in the brown binder. During the dissolution step will the lignin solution change color from brown to shiny black.
- After the lignin is completely dissolved, 1 liter of a foam dampening agent (Skumdaemper 11-10 from NCA-Verodan) is added. Temperature of the batch is maintained at 40°C.
- Then addition of 307,5 kg 35% hydrogen peroxide is started. The hydrogen peroxide is dosed at a rate of 200-300 liter/hour. First half of the hydrogen peroxide is added at a rate of 200 l/h where after the dosage rate is increased to 300 liter/hour.
- During the addition of hydrogen peroxide the temperature in the reaction mixture is controlled by heating or cooling in such a way that a final reaction temperature of 65°C is reached.
- After 15 min reaction at 65°C is the reaction mixture cooled to a temperature below 50°C. Hereby is a resin obtained having a COOH value of 1.2 mmol/g solids.
- The AOL used was prepared as described in the paragraph above using the amount of raw materials as specified in table 1. The AOL resin was mixed to binders by use of the raw materials specified in table 1.
- Stonewool products with Reference binders A1 to A5, B (reference products) and
binders 1 to 6 (inventive products) were made in a standard stonewool factory using the specified water type in table 1. - The stonewool products obtained were tested with respect to binder dry solid matter, loss of ignition and chloride content according to the methods described above as well as pH value. The results are also shown in Table 1.
Table 1 Material Ref A1 Ref A2 Ref A3 Ref A4 Ref A5 Ref B 1 2 3 4 5 6 AOL production: UPM biopiva 100 (kg), 67% - - - - - - 284 284 284 284 284 284 H2O2, 35% (kg) - - - - - - 57 57 57 57 57 57 NH4OH, 24.7% (kg) - - - - - - 162 53 53 53 53 53 water (kg) (tap water) - - - - - - 497 605 605 605 605 605 total AOL - - - - - - 1000 1000 1000 1000 1000 1000 Binder formulation: AOL (kg), 18,6% - - - - - - 883 883 883 883 883 883 PEG (kg) 100% - - - - - - 44 44 22 11 22 22 Primid XL-552 (kg), 100% - - - - - - 22 22 22 22 22 22 water for stone wool production rain water° process water process water osmosis water osmosis water°° rain water rain water rain water rain water rain water process water* process water** Results: Binder dry solid matter, 200C, 1h 42.5 42.5 42.5 42.5 42.5 20.0 19.0 19.0 19.0 19.0 19.0 19.0 Loss of ignition, stone wool product 2.7 3.8 3.4 3.5 3.2 3.8 3.1 3.2 3.1 3.3 4.0 4.0 Cl, mg/kg (EN 13468) 19 42.3 30.0 5.2 6.8 16 9.1 5.7 4.7 5.3 8.7 1.5 pH 9.7 9.5 9.8 9.9 9.6 6.8 8.6 8.7 8.9 9 8.5 8.5 ° chloride content of this rain water is 43 mg/L
°° chloride content of this osmosis water is <3 mg/L
* process water with higher chloride content (108 mg/L)
** process water with lower chloride content (50 mg/L)
Claims (15)
- A mineral fibre product, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- The mineral fibre product according to claim 1, wherein the mineral fibre product has a water leachable chloride content of less than 6 mg/kg in accordance with EN 13468:2001.
- The mineral fibre product according to claim 1 or claim 2, which is a thermal and/or acoustic insulation product.
- The mineral fibre product according to any of the preceding claims, wherein the mineral fibre product is a thermal and/or acoustic insulation for a pipe, a storage tank, a boiler, a vessel or a column, and/orwherein the mineral fibre product is in the form of a preformed pipe section, a wired mat or a slab, and/orwherein the mineral fibre product has a thickness in the range of 20 mm to 500 mm, preferably 30 mm to 300 mm, such as 50 mm to 150 mm.
- The mineral fibre product according to any of the preceding claims, wherein the mineral fibres are hydrophobically treated mineral fibres, preferably hydrophobically treated stone wool, wherein hydrophobic treatment is preferably carried out by treating the mineral fibres with at least one hydrophobic agent selected from mineral oils, siloxanes or silicon resins.
- The mineral fibre product according to any of the preceding claims, wherein the non-cured binder composition is an aqueous binder composition, wherein preferably at least part of the water or the total water contained in the aqueous binder composition is non-purified water, wherein the non-purified water is preferably selected from tap water, rain water, process water or a combination thereof.
- The mineral fibre product according to any of the preceding claims, wherein the non-cured binder composition comprises:- a component (i) in form of one or more oxidized lignins;- a component (ii) in form of one or more cross-linkers;- optionally a component (iii) in form of one or more plasticizers.
- The mineral fibre product according to any of the preceding claims, wherein the one or more oxidized lignins are oxidation products of a lignin being selected from the group of Kraft lignins, soda lignins, lignosulfonate lignins, organosolv lignins, lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof; and/or
wherein the one or more oxidized lignins are in form of one or more ammonia-oxidized lignins (AOL's). - The mineral fibre product according to any of the preceding claims, wherein the one or more oxidized lignins have a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of the one or more oxidized lignins.
- The mineral fibre product according to any of claims 7 to 9, wherein the component (ii) is in form of one or more cross-linkers selected froma) β-hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers, and/orb) multifunctional organic amines such as an alkanolamine, diamines, such as hexamethyldiamine, triamines, and/orc) an epoxidized oil based on fatty acid triglyceride or one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups, and/ord) a molecule having 3 or more epoxy groups, and/ore) one or more cross-linkers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines; and/orf) one more cross-linkers in form of fatty amides; and/org) one or more cross-linkers selected from the group consisting of dimethoxyethanal, glycolaldehyde, glyoxalic acid; and/orh) one or more cross-linkers selected from polyester polyols, such as polycaprolactone; and/ori) one or more cross-linkers selected from the group consisting of starch, modified starch, CMC; and/orj) one or more cross-linkers in form of aliphatic multifunctional carbodiimides; and/ork) one or more cross-linkers selected from melamine based cross-linkers, such as a hexakis(methylmethoxy)melamine (HMMM) based cross-linkers,wherein of one or more cross-linkers are preferably selected from β-hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers.
- The mineral fibre product according to any of the claims 7 to 10, wherein component (iii) is comprised in the non-cured binder composition in form of one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, and/or- one or more plasticizers selected from the group consisting of fatty alcohols, monohydroxy alcohols, such as pentanol, stearyl alcohol; and/or- one or more plasticizers selected from the group consisting of alkoxylates such as ethoxylates, such as butanol ethoxylates, such as butoxytriglycol; and/or- one or more plasticizers in form of propylene glycols; and/or- one or more plasticizers in form of glycol esters; and/or- one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and/or- one or more plasticizers selected from the group consisting of phenol derivatives, such as alkyl or aryl substituted phenols; and/or- one or more plasticizers selected from the group consisting of silanols, siloxanes; and/or- one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl and/or- sulfonates, phosphates such as tripolyphosphates; and/or- one or more plasticizers in form of hydroxy acids; and/or- one or more plasticizers selected from the group consisting of monomeric amides, such as acetamides, benzamide, fatty acid amides such as tall oil amides; and/or- one or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyldimethylammoniumchloride; and/or- one or more plasticizers selected from the group consisting of vegetable oils such as castor oil, palm oil, linseed oil, soybean oil; and/or- tall oil, and/or- one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils; and/or- one or more plasticizers selected from acid methyl esters; and/or- one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucoseamides, sucrose esters, sorbitan esters; and/or- one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers.
- A use of a mineral fibre product, preferably the mineral fibre product is as defined in any of claims 1 to 11, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, as a thermal and/or acoustic insulation, in particular a non-corrosive thermal and/or acoustic insulation, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
- The use according to claim 12, at temperatures in the range of -20 °C to 320 °C, preferably 0 °C to 200 °C, such as 50 °C to 175 °C.
- A method for the manufacture of a mineral fibre product, preferably the mineral fibre product is as defined in any of claims 1 to 11, comprising mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001,the method comprising the steps ofa) providing a non-cured aqueous binder composition comprising one or more oxidized lignins and water,b) contacting mineral fibres with the non-cured aqueous binder composition, andc) curing the binder composition in contact with the mineral fibers,wherein at least part of the water or the total water contained in the non-cured aqueous binder composition is non-purified water added, wherein the non-purified water is preferably selected from tap water, rain water, process water or a combination thereof,preferably the proportion of non-purified water added is in the range of 30 to 100 wt.-%, preferably 50 to 100 wt.-%, based on the total weight of water contained in the uncured binder composition, and/orthe water content in the uncured aqueous binder composition is in the range of 40 to 90 wt.-%, preferably 60 to 85 wt.-%, based on the total weight of the uncured aqueous binder composition.
- A hollow object, preferably selected from a pipe, a storage tank, a boiler, a vessel or a column, preferably a pipe, and/or wherein the hollow object is made of metal, wherein the metal is preferably selected from copper or steel, in particular carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low alloy steel, covered with a mineral fibre product, preferably the mineral fibre product is as defined in any of claims 1 to 11, as a thermal and/or acoustic insulation, wherein the mineral fibre product comprises mineral fibres bound by a cured binder composition, the non-cured binder composition comprising one or more oxidized lignins, wherein the mineral fibre product optionally has a water leachable chloride content of less than 10 mg/kg in accordance with EN 13468:2001.
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US5661213A (en) | 1992-08-06 | 1997-08-26 | Rohm And Haas Company | Curable aqueous composition and use as fiberglass nonwoven binder |
US5318990A (en) | 1993-06-21 | 1994-06-07 | Owens-Corning Fiberglas Technology Inc. | Fibrous glass binders |
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EP1086932A1 (en) | 1999-07-16 | 2001-03-28 | Rockwool International A/S | Resin for a mineral wool binder comprising the reaction product of an amine with a first and second anhydride |
EP1164163A1 (en) | 2000-06-16 | 2001-12-19 | Rockwool International A/S | Binder for mineral wool products |
EP1170265A1 (en) | 2000-07-04 | 2002-01-09 | Rockwool International A/S | Binder for mineral wool products |
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EP1382642A1 (en) | 2002-07-15 | 2004-01-21 | Rockwool International A/S | Formaldehyde-free aqueous binder composition for mineral fibers |
FR2853903B1 (en) | 2003-04-16 | 2005-05-27 | Saint Gobain Isover | MINERAL FIBER SIZING COMPOSITION COMPRISING A CARBOXYLIC POLYACIDE AND A POLYAMINE, PROCESS FOR PREPARATION, AND RESULTING PRODUCTS |
EP1669396A1 (en) | 2004-12-10 | 2006-06-14 | Rockwool International A/S | Aqueous binder for mineral fibers |
EP1741726A1 (en) | 2005-07-08 | 2007-01-10 | Rohm and Haas France SAS | Curable aqueous composition and use as water repellant fiberglass nonwoven binder |
EP1892225A1 (en) | 2006-08-23 | 2008-02-27 | Rockwool International A/S | Aqueous urea-modified binder for mineral fibres |
DE102009051885A1 (en) * | 2009-11-04 | 2011-05-05 | Blue Globe Energy Gmbh | Organo-mineral fertilizer produced by ammonium oxidation of lignin, comprising ammonium, normally hydrolyzable amide nitrogen and solid organically bonded nitrogen, useful for development or rehabilitation of sandy soils and fallow land |
FR2976584B1 (en) * | 2011-06-17 | 2014-12-12 | Saint Gobain Isover | SIZING COMPOSITION FOR MINERAL WOOL BASED ON SALT OF LIGNOSULPHONIC ACID AND OLIGOSACCHARIDE, AND INSULATING PRODUCTS OBTAINED |
US10475620B2 (en) * | 2015-01-27 | 2019-11-12 | Nanoscope Services Limited | Charged particle instruments |
EA034416B1 (en) * | 2015-01-30 | 2020-02-05 | Сэн-Гобэн Изовер | Insulating product |
EP3632866A1 (en) * | 2018-10-05 | 2020-04-08 | Rockwool International A/S | Aqueous binder composition |
-
2020
- 2020-04-03 CA CA3174088A patent/CA3174088A1/en active Pending
- 2020-04-03 PL PL20718606.5T patent/PL4127068T3/en unknown
- 2020-04-03 US US17/995,104 patent/US20230175178A1/en active Pending
- 2020-04-03 EP EP23212785.2A patent/EP4310062A3/en active Pending
- 2020-04-03 CN CN202080100991.4A patent/CN115605548A/en active Pending
- 2020-04-03 WO PCT/EP2020/059671 patent/WO2021197638A1/en active Application Filing
- 2020-04-03 EP EP20718606.5A patent/EP4127068B1/en active Active
- 2020-04-03 ES ES20718606T patent/ES2971295T3/en active Active
- 2020-04-03 HU HUE20718606A patent/HUE065024T2/en unknown
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EP4310062A2 (en) | 2024-01-24 |
EP4127068A1 (en) | 2023-02-08 |
EP4127068C0 (en) | 2023-12-13 |
WO2021197638A1 (en) | 2021-10-07 |
PL4127068T3 (en) | 2024-03-18 |
ES2971295T3 (en) | 2024-06-04 |
US20230175178A1 (en) | 2023-06-08 |
CN115605548A (en) | 2023-01-13 |
CA3174088A1 (en) | 2021-10-07 |
HUE065024T2 (en) | 2024-04-28 |
EP4310062A3 (en) | 2024-02-14 |
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